Sample records for carbon-carbon bond forming

Numerous enzymes have been found to catalyze additional and completely different types of reactions relative to the natural activity they evolved for. This phenomenon, called catalytic promiscuity, has proven to be a fruitful guide for the development of novel biocatalysts for organic synthesis purposes. As such, enzymes have been identified with promiscuous catalytic activity for, one or more, eminent types of carbon-carbonbond-forming reactions like aldol couplings, Michael(-type) additions, Mannich reactions, Henry reactions, and Knoevenagel condensations. This review focuses on enzymes that promiscuously catalyze these reaction types and exhibit high enantioselectivities (in case chiral products are obtained). PMID:25598537

Strategies for the formation of carbon-carbonbonds from the α-thioaryl carbonyl products of substituted lactams are described. Although direct functionalization is possible, a two step process of oxidation and magnesium-sulfoxide exchange has proven optimal. The oxidation step results in the formation of two diastereomers that exhibit markedly different levels of stability toward elimination, which is rationalized on the basis of quantum mechanical calculations and X-ray crystallography. Treatment of the sulfoxide with i-PrMgCl results in the formation of a magnesium enolate that will undergo an intramolecular Michael addition reaction to form two new stereogenic centers. The relationship between the substitution patterns of the sulfoxide substrate and the efficiency of the magnesium exchange reaction are also described. PMID:22023077

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbonbond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbonbond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbonbond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbonbond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbonbond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbonbond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

Carbon-carbonbond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their substrates, these reactions have been difficult to characterize. A CYP1A2-catalyzed carbon-carbonbond cleavage reaction is required for conversion of the prodrug nabumetone to its active form, 6-methoxy-2-naphthylacetic acid (6-MNA). Despite worldwide use of nabumetone as an anti-inflammatory agent, the mechanism of its carbon-carbonbond cleavage reaction remains obscure. With the help of authentic synthetic standards, we report here that the reaction involves 3-hydroxylation, carbon-carbon cleavage to the aldehyde, and oxidation of the aldehyde to the acid, all catalyzed by CYP1A2 or, less effectively, by other P450 enzymes. The data indicate that the carbon-carbonbond cleavage is mediated by the ferric peroxo anion rather than the ferryl species in the P450 catalytic cycle. CYP1A2 also catalyzes O-demethylation and alcohol to ketone transformations of nabumetone and its analogs. PMID:24584631

Carbon-carbonbond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their substrates, these reactions have been difficult to characterize. A CYP1A2-catalyzed carbon-carbonbond cleavage reaction is required for conversion of the prodrug nabumetone to its active form, 6-methoxy-2-naphthylacetic acid (6-MNA). Despite worldwide use of nabumetone as an anti-inflammatory agent, the mechanism of its carbon-carbonbond cleavage reaction remains obscure. With the help of authentic synthetic standards, we report here that the reaction involves 3-hydroxylation, carbon-carbon cleavage to the aldehyde, and oxidation of the aldehyde to the acid, all catalyzed by CYP1A2 or, less effectively, by other P450 enzymes. The data indicate that the carbon-carbonbond cleavage is mediated by the ferric peroxo anion rather than the ferryl species in the P450 catalytic cycle. CYP1A2 also catalyzes O-demethylation and alcohol to ketone transformations of nabumetone and its analogs. PMID:24584631

Covalent carbon-carbonbonds are hard to break. Their strength is evident in the hardness of diamonds and tensile strength of polymeric fibres; on the single-molecule level, it manifests itself in the need for forces of several nanonewtons to extend and mechanically rupture one bond. Such forces have been generated using extensional flow, ultrasonic irradiation, receding meniscus and by directly stretching a single molecule with nanoprobes. Here we show that simple adsorption of brush-like macromolecules with long side chains on a substrate can induce not only conformational deformations, but also spontaneous rupture of covalent bonds in the macromolecular backbone. We attribute this behaviour to the fact that the attractive interaction between the side chains and the substrate is maximized by the spreading of the side chains, which in turn induces tension along the polymer backbone. Provided the side-chain densities and substrate interaction are sufficiently high, the tension generated will be strong enough to rupture covalent carbon-carbonbonds. We expect similar adsorption-induced backbone scission to occur for all macromolecules with highly branched architectures, such as brushes and dendrimers. This behaviour needs to be considered when designing surface-targeted macromolecules of this type-either to avoid undesired degradation, or to ensure rupture at predetermined macromolecular sites.

A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact with a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.

Carbon-carbonbond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagents in chemical synthesis, a general catalytic methodology for enantioselective C-C formation has proven elusive, until now. Here, we report a copper-based chiral catalytic system that allows carbon-carbonbond formation via allylic alkylation with alkyllithium reagents, with extremely high enantioselectivities and able to tolerate several functional groups. We have found that both the solvent used and the structure of the active chiral catalyst are the most critical factors in achieving successful asymmetric catalysis with alkyllithium reagents. The active form of the chiral catalyst has been identified through spectroscopic studies as a diphosphine copper monoalkyl species.

An intramolecular σ-bond metathesis between carbon-carbon and silicon-silicon bonds took place on treatment of a disilane tethered to a cyclobutanone with a palladium(0) catalyst, furnishing a silaindane skeleton as well as an acylsilane functionality at once. PMID:22651103

A series of novel benzimidazolium salts (1-4) and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI) themed palladium N-heterocyclic carbene complexes [PdCl2(NHC)(Py)] (5-8), where NHC = 1-(N-methylphthalimide)-3-alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of (1)H and (13)C{(1)H} NMR, UV-vis (for 5-8), ESI-FTICR-MS (for 2, 4, 6-8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki-Miyaura cross-coupling (for 1-8) and arylation (for 5-8) reactions. As catalysts, they demonstrated a highly efficient route for the formation of asymmetric biaryl compounds even though they were used in very low loading. For example, all compounds displayed good catalytic activity for the C-C bond formation of 4-tert-butylphenylboronic acid with 4-chlorotoluene. PMID:26877810

Carbon-carbon (C-C) bondsform the backbone of many important molecules, including polymers, dyes and pharmaceutical agents. The development of new methods to create these essential connections in a rapid and practical fashion has been the focus of numerous organic chemists. This endeavour relies heavily on the ability to form C-C bonds in the presence of sensitive functional groups and congested structural environments. Here we report a chemical transformation that allows the facile construction of highly substituted and uniquely functionalized C-C bonds. Using a simple iron catalyst, an inexpensive silane and a benign solvent under ambient atmosphere, heteroatom-substituted olefins are easily reacted with electron-deficient olefins to create molecular architectures that were previously difficult or impossible to access. More than 60 examples are presented with a wide array of substrates, demonstrating the chemoselectivity and mildness of this simple reaction.

To improve the bonding strength of Sr and Na co-substituted hydroxyapatite (SNH) coatings for carbon/carbon composites, carbon/carbon composites are surface modified by micro-oxidation treatment. The micro-oxidation treatment could generate large number of pores containing oxygenic functional groups on the surface of carbon/carbon composites. SNH is nucleated on the inwall of the pores and form a flaky shape coating with 10-50 nm in thickness and 200-900 nm in width. The bonding strength between SNH coating and carbon/carbon composites increases from 4.27 ± 0.26 MPa to 10.57 ± 0.38 MPa after the micro-oxidation treatment. The promotion of bonding strength is mainly attributed to the pinning effect caused by the pores and chemical bonding generated by the oxygenic functional groups.

A strong bonding collagen film was successfully prepared on carbon/carbon (C/C) composites. The surface conditions of the modified C/C composites were detected by contact angle measurements, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectra. The roughness, optical morphology, bonding strength and biocompatibility of collagen films at different pH values were detected by confocal laser scanning microscope (CLSM), universal test machine and cytology tests in vitro. After a 4-h modification in 30% H2O2 solution at 100 °C, the contact angle on the surface of C/C composites was decreased from 92.3° to 65.3°. Large quantities of hydroxyl, carboxyl and carbonyl functional groups were formed on the surface of the modified C/C composites. Then a dense and continuous collagen film was prepared on the modified C/C substrate. Bonding strength between collagen film and C/C substrate was reached to 8 MPa level when the pH value of this collagen film was 2.5 after the preparing process. With 2-day dehydrathermal treatment (DHT) crosslinking at 105 °C, the bonding strength was increased to 12 MPa level. At last, the results of in vitro cytological test showed that this collagen film made a great improvement on the biocompatibility on C/C composites.

The metal-induced coupling of tertiary diamondoid bromides gave highly sterically congested hydrocarbon (hetero)dimers with exceptionally long central C-C bonds of up to 1.71 Å in 2-(1-diamantyl)[121]tetramantane. Yet, these dimers are thermally very stable even at temperatures above 200 °C, which is not in line with common C-C bond length versus bond strengths correlations. We suggest that the extraordinary stabilization arises from numerous intramolecular van der Waals attractions between the neighboring H-terminated diamond-like surfaces. The C-C bond rotational dynamics of 1-(1-adamantyl)diamantane, 1-(1-diamantyl)diamantane, 2-(1-adamantyl)triamantane, 2-(1-diamantyl)triamantane, and 2-(1-diamantyl)[121]tetramantane were studied through variable-temperature (1)H- and (13)C NMR spectroscopies. The shapes of the inward (endo) CH surfaces determine the dynamic behavior, changing the central C-C bond rotation barriers from 7 to 33 kcal mol(-1). We probe the ability of popular density functional theory (DFT) approaches (including BLYP, B3LYP, B98, B3LYP-Dn, B97D, B3PW91, BHandHLYP, B3P86, PBE1PBE, wB97XD, and M06-2X) with 6-31G(d,p) and cc-pVDZ basis sets to describe such an unusual bonding situation. Only functionals accounting for dispersion are able to reproduce the experimental geometries, while most DFT functionals are able to reproduce the experimental rotational barriers due to error cancellations. Computations on larger diamondoids reveal that the interplay between the shapes and the sizes of the CH surfaces may even allow the preparation of open-shell alkyl radical dimers (and possibly polymers) that are strongly held together exclusively by dispersion forces. PMID:22835264

High temperature adhesives with good thermal conductivity, mechanical performance, and long term durability are crucial for the assembly of heat rejection system components for space exploration missions. In the present study, commercially available adhesives were used to bond high conductivity carbon-carbon composites to titanium sheets. Bonded pieces were also exposed to high (530 to 600 Kelvin for 24 hours) and low (liquid nitrogen 77K for 15 minutes) temperatures to evaluate the integrity of the bonds. Results of the microstructural characterization and tensile shear strengths of bonded specimens will be reported. The effect of titanium surface roughness on the interface microstructure will also be discussed.

The carbon-carbon single bond is of central importance in organic chemistry. When the molecular mechanics MM4 force field was developed beginning in the early 1990s, C-C bond lengths were not known very reliably for many important molecules, and bond lengths greater than 1.6 Å were quite poorly known experimentally. Quantum-mechanically computed values could not yet be obtained with useful accuracy in a general way. This paper examines structures now available from experiment and quantum-mechanical computations and extends the fit of the MM4 methodology to include new bond distances as long as 1.71 Å. PMID:27164310

Most of the efforts of organic chemists have been directed to the development of creative strategies to build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. In this Review, we show an alternative approach where challenging molecular skeletons could be prepared through selective cleavage of carbon-carbonbonds. We demonstrate that it has the potential to be a general principle in organic synthesis for the regio-, diastereo-, and even enantioselective preparation of adducts despite the fact that C-C single bonds are among the least reactive functional groups. The development of such strategies may have an impact on synthesis design and can ultimately lead to new selective and efficient processes for the utilization of simple hydrocarbons. PMID:25266824

The methanol-to-olefin (MTO) process allows the conversion of methanol/dimethyl ether into olefins on acidic zeolites via the so-called hydrocarbon pool mechanism. However, the site and mechanism of formation of the first carbon-carbonbond are still a matter of debate. Here, we show that the Lewis acidic Al sites on the 110 facet of γ-Al2O3 can readily activate dimethyl ether to yield CH4, alkenes, and surface formate species according to spectroscopic studies combined with a computational approach. The carbon-carbonforming step as well as the formation of methane and surface formate involves a transient oxonium ion intermediate, generated by a hydrogen transfer between surface methoxy species and coordinated methanol on adjacent Al sites. These results indicate that extra framework Al centers in acidic zeolites, which are associated with alumina, can play a key role in the formation of the first carbon-carbonbond, the initiation step of the industrial MTO process. PMID:27162986

Recent publications have brought renewed interest to the quest for homogeneous catalytic activation of carbon-carbonbonds. However, except for a few reports of biphenylene cleavage, the mechanism and scope of aryl-aryl C-C bond activation remains relatively uninvestigated. In the hope of overcoming the obstacle of weak M-C bonds, we used a rhodium system that should provide a thermodynamically favored C-C cleaved complex by making strong metal-aryl bonds. Reaction of (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(Ph)(H) (1) with 1.5 equiv of biphenylene in cyclohexane-d[sub 12] at 65[degree]C resulted in the quantitative formation of (CC[sub 5]Me[sub 5])Rh(PMe[sub 3]) (biphenylenyl(H)) (2), along with a small amount of a red complex. The cleavage of the well-hidden carbon-carbonbond of biphenylene described relies both on a strained four-membered ring and on the formation of a stable pentametallacycle. The results show that C-H activation and [eta][sup 2] coordination are probably involved in the process leading to C-C bond cleavage, and valuable information can be obtained from studies of this system. 21 refs., 1 fig.

OleT is a cytochrome P450 that catalyzes the hydrogen peroxide-dependent metabolism of Cn chain-length fatty acids to synthesize Cn-1 1-alkenes. The decarboxylation reaction provides a route for the production of drop-in hydrocarbon fuels from a renewable and abundant natural resource. This transformation is highly unusual for a P450, which typically uses an Fe(4+)-oxo intermediate known as compound I for the insertion of oxygen into organic substrates. OleT, previously shown to form compound I, catalyzes a different reaction. A large substrate kinetic isotope effect (≥8) for OleT compound I decay confirms that, like monooxygenation, alkene formation is initiated by substrate C-H bond abstraction. Rather than finalizing the reaction through rapid oxygen rebound, alkene synthesis proceeds through the formation of a reaction cycle intermediate with kinetics, optical properties, and reactivity indicative of an Fe(4+)-OH species, compound II. The direct observation of this intermediate, normally fleeting in hydroxylases, provides a rationale for the carbon-carbon scission reaction catalyzed by OleT. PMID:27555591

The elementary reactions leading to the formation of the first carbon-carbonbond during early stages of the zeolite-catalyzed methanol conversion into hydrocarbons were identified by combining kinetics, spectroscopy, and DFT calculations. The first intermediates containing a C-C bond are acetic acid and methyl acetate, which are formed through carbonylation of methanol or dimethyl ether even in presence of water. A series of acid-catalyzed reactions including acetylation, decarboxylation, aldol condensation, and cracking convert those intermediates into a mixture of surface bounded hydrocarbons, the hydrocarbon pool, as well as into the first olefin leaving the catalyst. This carbonylation based mechanism has an energy barrier of 80 kJ mol(-1) for the formation of the first C-C bond, in line with a broad range of experiments, and significantly lower than the barriers associated with earlier proposed mechanisms. PMID:27037603

The cleavage of carbon-carbon (C-C) bonds by transition metals is of great interest, especially as this transformation can be used to produce fuels and other industrially important chemicals from natural resources such as petroleum and biomass. Carbon-carbonbonds are quite stable and are consequently unreactive under many reaction conditions. In the industrial naphtha hydrocracking process, the aromatic carbon skeleton of benzene can be transformed to methylcyclopentane and acyclic saturated hydrocarbons through C-C bond cleavage and rearrangement on the surfaces of solid catalysts. However, these chemical transformations usually require high temperatures and are fairly non-selective. Microorganisms can degrade aromatic compounds under ambient conditions, but the mechanistic details are not known and are difficult to mimic. Several transition metal complexes have been reported to cleave C-C bonds in a selective fashion in special circumstances, such as relief of ring strain, formation of an aromatic system, chelation-assisted cyclometallation and β-carbon elimination. However, the cleavage of benzene by a transition metal complex has not been reported. Here we report the C-C bond cleavage and rearrangement of benzene by a trinuclear titanium polyhydride complex. The benzene ring is transformed sequentially to a methylcyclopentenyl and a 2-methylpentenyl species through the cleavage of the aromatic carbon skeleton at the multi-titanium sites. Our results suggest that multinuclear titanium hydrides could serve as a unique platform for the activation of aromatic molecules, and may facilitate the design of new catalysts for the transformation of inactive aromatics.

The cleavage of carbon-carbon (C-C) bonds by transition metals is of great interest, especially as this transformation can be used to produce fuels and other industrially important chemicals from natural resources such as petroleum and biomass. Carbon-carbonbonds are quite stable and are consequently unreactive under many reaction conditions. In the industrial naphtha hydrocracking process, the aromatic carbon skeleton of benzene can be transformed to methylcyclopentane and acyclic saturated hydrocarbons through C-C bond cleavage and rearrangement on the surfaces of solid catalysts. However, these chemical transformations usually require high temperatures and are fairly non-selective. Microorganisms can degrade aromatic compounds under ambient conditions, but the mechanistic details are not known and are difficult to mimic. Several transition metal complexes have been reported to cleave C-C bonds in a selective fashion in special circumstances, such as relief of ring strain, formation of an aromatic system, chelation-assisted cyclometallation and β-carbon elimination. However, the cleavage of benzene by a transition metal complex has not been reported. Here we report the C-C bond cleavage and rearrangement of benzene by a trinuclear titanium polyhydride complex. The benzene ring is transformed sequentially to a methylcyclopentenyl and a 2-methylpentenyl species through the cleavage of the aromatic carbon skeleton at the multi-titanium sites. Our results suggest that multinuclear titanium hydrides could serve as a unique platform for the activation of aromatic molecules, and may facilitate the design of new catalysts for the transformation of inactive aromatics. PMID:25164752

Tandem reactions using base-promoted processes have been developed for the synthesis of xanthone and chromone derivatives. The first examples of base-promoted insertion reactions of isolated carbon-carbon triple bonds into carbon-carbon σ-bonds have been reported. Using these approaches, polycyclic structures can be prepared. This reaction has the potential to become a general synthetic protocol for the preparation of multi-substituted xanthones and chromones due to the abundance of easily accessible starting materials possessing diverse substituent groups. PMID:27460875

N-acyliminium ions are useful reactive synthetic intermediates in a variety of important carbon-carbonbondforming and cyclisation strategies in organic chemistry. The advent of an electrochemical anodic oxidation of unfunctionalised amides, more commonly known as the Shono oxidation, has provided a complementary route to the C-H activation of low reactivity intermediates. In this article, containing over 100 references, we highlight the development of the Shono-type oxidations from the original direct electrolysis methods, to the use of electroauxiliaries before arriving at indirect electrolysis methodologies. We also highlight new technologies and techniques applied to this area of electrosynthesis. We conclude with the use of this electrosynthetic approach to challenging syntheses of natural products and other complex structures for biological evaluation discussing recent technological developments in electroorganic techniques and future directions. PMID:25670975

New carbon-carbonbond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.

Remarkable innovations have been made in the field of olefin metathesis due to the design and preparation of new catalysts. Ethenolysis, which is cross-metathesis with ethylene, represents one catalytic transformation that has been used with the purpose of cleaving internal carbon-carbon double bonds. The objectives were either the ring opening of cyclic olefins to produce dienes or the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner. This Review summarizes several aspects of this reaction: the catalysts, their degradation in the presence of ethylene, some parameters driving their productivity, the side reactions, and the applications of ethenolysis in organic synthesis and in potential industrial applications. PMID:27359344

Here, we demonstrate that merging photoredox catalysis with Lewis acid catalysis provides a fundamentally new activation mode of C-C triple bonds, to achieve the bond-forming reaction of alkynes with weak nucleophiles. Using a synergistic merger of Eosin Y and Cu(OTf)2, a highly efficient cyclization reaction of arene-ynes was developed. PMID:27432542

The nickel alkyne complexes (dippe)Ni(PhC{triple{underscore}bond}CPh), 2, (dippe) Ni(MeO{sub 2}CC{triple{underscore}bond}CCO{sub 2}Me), 3, (dippe)Ni(CH{sub 3}OCH{sub 2}C{triple{underscore}bond}CCH{sub 2}OCH{sub 3}), 4, and (dippe)Ni(CF{sub 3}C{triple{underscore}bond}CCF{sub 3}), 5, were synthesized (dippe = bis(diisopropylphosphino)ethane) and characterized by {sup 1}H, {sup 31}P, and {sup 13}C{l{underscore}brace}{sup 1}H{r{underscore}brace} NMR spectroscopy. Complexes 1, 2, and 3 were characterized by X-ray crystallography. The thermolysis of complex 1 or 2 (120 C) in the presence of excess biphenylene and excess alkyne results in very slow catalytic formation of the corresponding 9,10-disubstituted phenanthrene. However, addition of {approximately}6 mol % O{sub 2} (based on the metal complex) to the reaction mixture results in an acceleration in catalysis at lower temperatures ({approximately}70--80 C). The thermolysis of complexes 3 or 4 with excess biphenylene and excess alkyne leads to the alkyne cyclotrimerization product as the major organic species formed in the reaction. Fluorenone was catalytically produced by heating (dippe)Ni(CO){sub 2}, biphenylene, and CO. Catalytic insertion of 2,6-xylylisocyanide into the strained C-C bond of biphenylene was also achieved by heating (dippe)Ni(2,6-xylylisocyanide){sub 2}, excess biphenylene, and 2,6-xylylisocyanide. Mechanistic schemes are proposed for these reactions.

Aliphatic oxidative carbon-carbonbond cleavage reactions involving Cu(II) catalysts and O2 as the terminal oxidant are of significant current interest. However, little is currently known regarding how the nature of the Cu(II) catalyst, including the anions present, influence the reaction with O2. In previous work, we found that exposure of the Cu(II) chlorodiketonate complex [(6-Ph2TPA)Cu(PhC(O)CClC(O)Ph)]ClO4 (1) to O2 results in oxidative aliphatic carbon-carbonbond cleavage within the diketonate unit, leading to the formation of benzoic acid, benzoic anhydride, benzil, and 1,3-diphenylpropanedione as organic products. Kinetic studies of this reaction revealed a slow induction phase followed by a rapid decay of the absorption features of 1. Notably, the induction phase is not present when the reaction is performed in the presence of a catalytic amount of chloride anion. In the studies presented herein, a combination of spectroscopic (UV-vis, EPR) and density functional theory (DFT) methods have been used to examine the chloride and benzoate ion binding properties of 1 under anaerobic conditions. These studies provide evidence that each anion coordinates in an axial position of the Cu(II) center. DFT studies reveal that the presence of the anion in the Cu(II) coordination sphere decreases the barrier for O2 activation and the formation of a Cu(II)-peroxo species. Notably, the chloride anion more effectively lowers the barrier associated with O-O bond cleavage. Thus, the nature of the anion plays an important role in determining the rate of reaction of the diketonate complex with O2. The same type of anion effects were observed in the O2 reactivity of the simple Cu(II)-bipyridine complex [(bpy)Cu(PhC(O)C(Cl)C(O)Ph)ClO4] (3). PMID:27377103

Carbon-atom extrusion from the ipso-position of a halobenzene ring (C6 H5 X; X=F, Cl, Br, I) and its coupling with a methylene ligand to produce acetylene is not confined to [LaCH2 ](+) ; also, the third-row transition-metal complexes [MCH2 ](+) , M=Hf, Ta, W, Re, and Os, bring about this unusual transformation. However, substrates with substituents X=CN, NO2 , OCH3 , and CF3 are either not reactive at all or give rise to different products when reacted with [LaCH2 ](+) . In the thermal gas-phase processes of atomic Ln(+) with C7 H7 Cl substrates, only those lanthanides with a promotion energy small enough to attain a 4f(n) 5d(1) 6s(1) configuration are reactive and form both [LnCl](+) and [LnC5 H5 Cl](+) . Branching ratios and the reaction efficiencies of the various processes seem to correlate with molecular properties, like the bond-dissociation energies of the C-X or M(+) -X bonds or the promotion energies of lanthanides. PMID:26875940

Three novel fluorescent molecules with carbon-carbon triple bonds 2TBEA, 2TBDA and TEPEB are successfully designed and synthesized. Their thermal, photophysical, electrochemical, electronic and thin-film self-assembly properties were characterized. Three dyes showed typical photoluminescence (PL) emission behaviors, the PL intensities firstly increased and then decreased with gradually decreasing concentration. The appealing fluorescence properties indicated that three dyes could be used as good fluorescent materials. Additionally, the thin-film self-assembly behaviors of three dyes were also investigated. The microstructures of their optical microscopy (OM) images exhibited high flexibility. Furthermore, SEM and AFM surface morphology of these self-assembly nanostructures revealed that three well-defined long-range order of rod-like and tube-like self-assembly systems exhibited interesting morphology properties. Therefore, three compounds may be of great interest for the development of organic thin-film materials.

Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C-C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through (13)C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives. PMID:25355907

Grand Cleft Oxo: Levulinate, available from biomass, is oxidized into succinate through manganese(III)-catalyzed selective cleavage of CC bonds with molecular oxygen. In addition to levulinate, a wide range of aliphatic methyl ketones also undergo oxidative CC bond cleavage at the carbonyl group. This procedure offers a route to valuable dicarboxylic acids from biomass resources by nonfermentive approaches. PMID:23922234

Natural products containing phosphorus-carbon bonds have found widespread use in medicine and agriculture1. One such compound, phosphinothricin tripeptide (PTT), contains the unusual amino acid phosphinothricin (PT) attached to two alanine residues (Fig. 1). Synthetic PT (glufosinate) is a component of two top-selling herbicides (Basta® and Liberty®), and is widely used with resistant transgenic crops including corn, cotton and canola. Recent genetic and biochemical studies showed that during PTT biosynthesis 2-hydroxyethylphosphonate (HEP) is converted to hydroxymethylphosphonate (HMP) (Fig. 1)2. Reported here are the in vitro reconstitution of this unprecedented C(sp3)-C(sp3) bond cleavage reaction and X-ray crystal structures of the enzyme. The protein is a mononuclear non-heme iron(II)-dependent dioxygenase that converts HEP to HMP and formate. In contrast to most other members of this family, the oxidative consumption of HEP does not require additional cofactors or the input of exogenous electrons. The current study expands the scope of reactions catalyzed by the 2-His-1-carboxylate mononuclear non-heme iron family of enzymes. PMID:19516340

Natural products containing phosphorus-carbon bonds have found widespread use in medicine and agriculture. One such compound, phosphinothricin tripeptide, contains the unusual amino acid phosphinothricin attached to two alanine residues. Synthetic phosphinothricin (glufosinate) is a component of two top-selling herbicides (Basta and Liberty), and is widely used with resistant transgenic crops including corn, cotton and canola. Recent genetic and biochemical studies showed that during phosphinothricin tripeptide biosynthesis 2-hydroxyethylphosphonate (HEP) is converted to hydroxymethylphosphonate (HMP). Here we report the in vitro reconstitution of this unprecedented C(sp{sup 3})-C(sp{sup 3}) bond cleavage reaction and X-ray crystal structures of the enzyme. The protein is a mononuclear non-haem iron(II)-dependent dioxygenase that converts HEP to HMP and formate. In contrast to most other members of this family, the oxidative consumption of HEP does not require additional cofactors or the input of exogenous electrons. The current study expands the scope of reactions catalysed by the 2-His-1-carboxylate mononuclear non-haem iron family of enzymes.

Catalytic hydroalkylation of an alkyne with methyl ether was accomplished. Intramolecular addition of the C-H bond of a methoxy group in 1-methoxy-2-(arylethynyl)benzenes across a carbon-carbon triple bond took place efficiently either in toluene at 110 °C or in p-xylene at 135 °C in the presence of an iridium catalyst. The initial 5-exo cyclization products underwent double-bond migration during the reaction to give 3-(arylmethyl)benzofurans in high yields. PMID:27168516

Clear evidence for the existence of intermolecular carbon-carbon (C···C), nitrogen-nitrogen (N···N) and oxygen-oxygen (O···O) interactions between atoms in similar chemical environments in homogeneous dimers of organic dipolar molecules has been obtained from molecular orbital (MO), natural bond orbital (NBO) and atoms-in-molecule (AIM) electron density analyses at the M06L/6-311++G(d,p) level of density functional theory (DFT). These X···X type interactions are mainly the result of local polarization effects, causing segregation of electron-rich and electron-deficient regions in the X atoms, leading to complementary electrostatic interactions. NBO analysis provides evidence of charge transfer between the two X atoms. Even in symmetrical molecules such as acetylene, induced dipoles in the dimer create C···C bonding interactions. The strength of this type of interaction increases with increase in the dipole moment of the molecule. Energy decomposition analysis (EDA) shows that the electrostatic component of the interaction energy (Eint) is very high, up to 95.86%. The C···C interactions between similar carbon atoms are located for several crystal structures obtained from the literature. In addition, MO, AIM and electrostatic potential analyses support interactions between similar oxygen (O···O) and nitrogen (N···N) atoms in a variety of molecular dimers. Good prediction of Eint is achieved in terms of the total gain in electron density at non-covalently interacting intermolecular bonds (∑ρ) and the monomer dipole moment (μ). A rigorously tested QSAR equation has been derived to predict Eint for all dimer systems: Eint (kcal mol(-1)) = -138.395∑ρ(au) - 0.551μ (Debye). This equation suggests that the polarization-induced bonding interaction between atoms in a similar chemical environment could well be a general chemical phenomenon. The results have been further validated by different density functional methods and also by G3MP2 method

Laboratory experiments carried out under plausible prebiotic conditions (under conditions that might have occurred at primitive deep-sea hydrothermal vents) in water and involving constituents that occur in the vicinity of submarine hydrothermal vents (e.g., CO, H2S, NiS) have disclosed an iterative Ni-catalyzed pathway of C-C bond formation. This pathway leads from CO to various organic molecules that comprise, notably, thiols, alkylmono- and disulfides, carboxylic acids, and related thioesters containing up to four carbon atoms. Furthermore, similar experiments with organic compounds containing various functionalities, such as thiols, carboxylic acids, thioesters, and alcohols, gave clues to the mechanisms of this novel synthetic process in which reduced metal species, in particular Ni(0), appear to be the key catalysts. Moreover, the formation of aldehydes (and ketones) as labile intermediates via a hydroformylation-related process proved to be at the core of the chain elongation process. Since this process can potentially lead to organic compounds with any chain length, it could have played a significant role in the prebiotic formation of lipidic amphiphilic molecules such as fatty acids, potential precursors of membrane constituents.

Aldehydes possess relatively high chemical energy, which is the driving force for disproportionation reactions such as Cannizzaro and Tishchenko reactions. Generally, this energy is wasted if aldehydes are transformed into carboxylic acids with a sacrificial oxidant. Here, we describe a cascade reaction in which the surplus energy of the transformation is liberated as molecular hydrogen for the oxidation of heptanal to heptanoic acid by water, and the carboxylic acid is transformed into potentially industrially relevant symmetrical ketones by ketonic decarboxylation. The cascade reaction is catalyzed by monoclinic zirconium oxide (m-ZrO2 ). The reaction mechanism has been studied through cross-coupling experiments between different aldehydes and acids, and the final symmetrical ketones are formed by a reaction pathway that involves the previously formed carboxylic acids. Isotopic studies indicate that the carboxylic acid can be formed by a hydride shift from the adsorbed aldehyde on the metal oxide surface in the absence of noble metals. PMID:27539722

Recently we have shown advances from reactions of O(^3P) with both, l ong-chain hydrocarbons and refinery residuum. The oxidation products of t he process, a mixture of alcohols, epoxides and carbonyl compounds, might have potential properties as additives in formulating fuels. This work s hows the results of the interactions of an oxygen plasma with double bond s, both olefin and aromatic, in the same compound. The reactions have bee n carried out by making the plasma, created by a high voltage glow discha rge, reach the low vapor pressure surface of liquid 4-phenyl-1-butene. Th is (3 mL) was cooled down to -45 ^oC in a glass reactor, applied power was 24 W, at an oxygen pressure of 20 Pa. Products were analyzed by IR, N MR and mass spectroscopies. Conversions were studied as a function of the reaction time, this ranging from 5 to 120 minutes. At short times the O( ^3P) atoms produced in the discharge only reacted with the alkene fra ction of the hydrocarbon, 4-phenyl-1,2-epoxibutane (52%) and 4-phenyl-bu tanal (48%) being the products. Reactions on the benzene ring were obser ved from about 30 minutes on, the corresponding phenols having being prod uced at ratios ortho:para:meta :: 4:1:0.7. At 120 minutes, the ol efin have been completely oxidized and a low fraction of the non-equivale nt two methylene groups have reacted to produce alcohols and ketones.

Ene-amides have been explored as ligands and substrates for oxidative coupling. Treatment of CrCl2, Cl2Fe(PMe3)2, and Cl2Copy4 with 2 equiv of {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}Li afforded pseudosquare planar {η(3)-C,C,N-(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}2Cr (1-Cr, 78%), trigonal {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}2Fe(PMe3) (2-Fe, 80%), and tetrahedral {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}2Co(py)2 (3-Co, 91%) in very good yields. The addition of CrCl3 to 1-Cr, and FeCl3 to 2-Fe, afforded oxidatively triggered C-C bond formation as rac-2,2'-di(2,6-(i)Pr2C6H3N═)2dicyclohexane (EA2) was produced in modest yields. Various lithium ene-amides were similarly coupled, and the mechanism was assessed via stoichiometric reactions. Some ferrous compounds (e.g., 2-Fe, FeCl2) were shown to catalyze C-arylation of {(2,6-(i)Pr2C6H3)(1-(c)Hexenyl)N}Li with PhBr, but the reaction was variable. Structural characterizations of 1-Cr, 2-Fe, and 3-Co are reported. PMID:27064509

An unusual intermolecular carbon-carbon short contact, observed previously in the crystal structure of the copper complex of pyridoxal-5-phosphate- pyridoxamine-5-phospate Schiff base, was investigated from a standpoint of quantum chemistry by DFT calculations with plane wave basis sets. The DFT-optimized structure qualitatively reproduced the short contact (2.6-2.8 Å) of the intermolecular carbon-carbon pairs for the dimer of the copper complexes in the unit cell, compared to that (∼2.3 Å) of the X-ray diffraction data. By the occupied and unoccupied orbitals, the dimer showed the in-phase and out-of-phase interactions along the direction of the intermolecular distance. The dimer of the copper complexes was confirmed as the stable intermediate between nonbonding and σ-covalent bonding by the electronic energy curve along the distance of the monomers. PMID:25559884

We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5(+), is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5(+) → C3H4(+) + H. Approximately 80% of the reaction products are ascribed to charge transfer, with ∼40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbonbonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5(+) complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5(+) complex. More than 75% of the nascent C4H3(+) products decay by C-H bond cleavage to yield a C4H2(+) species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5(+) adduct that is produced when the p-orbital containing the unpaired electron on C(+) overlaps with the unpaired spin density on the terminal carbon atoms in allyl. Product formation then occurs by 1,2-elimination of molecular hydrogen from the cyclic intermediate to form a planar cyclic C4H3(+) product. The large rearrangement in geometry as the C4H3(+) products are formed is consistent with high vibrational excitation in that product and supports the observation that the majority of those products decay to form the C4H2(+) species. PMID:27434380

Electron-rich alkynes, such as ynamines, ynamides, and ynol ethers, are functional groups that possess significant potential in organic chemistry for the formation of carbon-carbonbonds. While the synthetic utility of ynamides has recently been expanded considerably, 1-alkynyl ethers, which possess many of the reactivity features of ynamides, have traditionally been far less investigated because of concerns about their stability. Like ynamides, ynol ethers are relatively unhindered to approach by functional groups present in the same or different molecules because of their linear geometry, and they can potentially form up to four new bonds in a single transformation. Ynol ethers also possess unique reactivity features that make them complementary to ynamides. Research over the past decade has shown that ynol ethers formed in situ from stable precursors engage in a variety of useful carbon-carbonbond-forming processes. Upon formation at -78 °C, allyl alkynyl ethers undergo a rapid [3,3]-sigmatropic rearrangement to form allyl ketene intermediates, which may be trapped with alcohol or amine nucleophiles to form γ,δ-unsaturated carboxylic acid derivatives. The process is stereospecific, takes place in minutes at cryogenic temperatures, and affords products containing (quaternary) stereogenic carbon atoms. Trapping of the intermediate allyl ketene with carbonyl compounds, epoxides, or oxetanes instead leads to complex α-functionalized β-, γ-, or δ-lactones, respectively. [3,3]-Sigmatropic rearrangement of benzyl alkynyl ethers also takes place at temperatures ranging from -78 to 60 °C to afford substituted 2-indanones via intramolecular carbocyclization of the ketene intermediate. tert-Butyl alkynyl ethers containing pendant di- and trisubstituted alkenes and enol ethers are stable to chromatographic isolation and undergo a retro-ene/[2 + 2] cycloaddition reaction upon mild thermolysis (90 °C) to afford cis-fused cyclobutanones and donor

Oxidative C-H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C-C bond formation via C-H transformation and production of functionalized graphene. PMID:27181191

Ethylene, the simplest alkene, is the most abundantly synthesized organic molecule by volume. It is readily incorporated into transitionmetal–catalyzed carbon-carbonbond-forming reactions through migratory insertions into alkylmetal intermediates. Because of its D2h symmetry, only one insertion outcome is possible. This limits byproduct formation and greatly simplifies analysis. As described within this Minireview, many carbon–carbon bond-forming reactions incorporate a molecule (or more) of ethylene at ambient pressure and temperature. In many cases, a useful substituted alkene is incorporated into the product. PMID:24105881

The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress has been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A

Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed. These results inspired the development of a new Pd-catalyzed reductive coupling reaction of alkenes and organometallic reagents that generates a new carbon-carbonbond. Optimization of the conditions for the coupling of both organostannanes and organoboronic esters is described and the initial scope of the transformation is presented. Additionally, several mechanistic experiments are outlined and support the rationale for the development of the reaction based upon coupling alcohol oxidation to alkene functionalization. PMID:20161306

1. Program goals addressed during this period. Experimental work was directed at formation of a low-stress bond between carbon- carbon and aluminum, with the objective of minimizing the heating of the aluminum substrate, thereby minimizing stresses resulting from the coefficient of thermal expansion (CTE) difference between the aluminum and carbon-carbon. A second objective was to form a bond between carbon-carbon and aluminum with good thermal conductivity for electronic thermal management (SEM-E) application. 2. Substrates and joining materials selected during this period. Carbon-Carbon Composite (CCC) to Aluminum. CCC (Cu coated) to Aluminum. Soldering compounds based on Sn/Pb and Sn/Ag/Cu/Bi compositions. 3. Soldering experiments performed. Conventional techniques. High Energy Electron Beam (HEEB) process.

Alkylnitriles are one of the most ubiquitous nitrogen-containing chemicals and are widely employed in reactions which result in nitrile-group conversion into other functionalities. Nevertheless, their use as carbon pronucleophiles in carbon-carbonbond-forming reactions has been hampered by difficulties associated mainly with the catalytic generation of active species, that is, α-cyano carbanions or metalated nitriles. Recent investigations have addressed this challenge and have resulted in different modes of alkylnitrile activation. This review illustrates these findings, which have set the foundation for the development of practical and conceptually new catalytic, direct cyanoalkylation methodologies. PMID:26387483

Lanthanide-catalyzed alkynyl exchange through C-C single-bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex is proposed as a key intermediate, which undergoes unprecedented reversible β-alkynyl elimination followed by alkynyl exchange and imine reinsertion. The in situ homo- and cross-dimerization of the liberated alkyne can serve as an additional driving force to shift the metathesis equilibrium to completion. This reaction is formally complementary to conventional alkyne metathesis and allows the selective transformation of internal propargylamines into those bearing different substituents on the alkyne terminus in moderate to excellent yields under operationally simple reaction conditions. PMID:27510403

Generation of the 16-electron fragment {l_brace}[HB(3,5-dimethylpyrazolyl){sub 3}]Rh(CNCH{sub 2}CMe{sub 3}){r_brace} (Tp{prime}RhL) in the presence of cyclopropane results in C-H activation of the hydrocarbon. The cyclopropyl hydride complex rearranges in benzene solvent to the metallacyclobutane complex Tp{prime}Rh(CNCH{sub 2}CMe{sub 3})(CH{sub 2}CH{sub 2}CH{sub 2}). Thermolysis of the rhodacyclobutane complex produces an {eta}{sup 2}-propylene complex. The related complex Tp{prime}Rh(CN-2,6-xylyl)(C{sub 2}H{sub 4}) has been structurally characterized and displays {eta}{sup 3}-Tp{prime} coordination, both in the solid state and in solution. Thermolysis of the rhodacyclobutane complex in the presence of neopentyl isocyanide leads to insertion of isocyanide into both Rh-C bonds of the metallacycle. Cyclobutane undergoes C-H but not C-C bond cleavage.

A method for joining carbon-carbon composites to metals by brazing. Conventional brazing of recently developed carbon-bonded carbon fiber (CBCF) material to a metal substrate is limited by the tendency of the braze alloy to ``wick`` into the CBCF composite rather than to form a strong bond. The surface of the CBCF composite that is to be bonded is first sealed with a fairly dense carbonaceous layer achieved by any of several methods. The sealed surface is then brazed to the metal substrate by vacuum brazing with a Ti-Cu-Be alloy. 1 fig.

A method for joining carbon-carbon composites to metals by brazing. Conventional brazing of recently developed carbon-bonded carbon fiber (CBCF) material to a metal substrate is limited by the tendency of the braze alloy to "wick" into the CBCF composite rather than to form a strong bond. The surface of the CBCF composite that is to be bonded is first sealed with a fairly dense carbonaceous layer achieved by any of several methods. The sealed surface is then brazed to the metal substrate by vacuum brazing with a Ti-Cu-Be alloy.

A family of novel linear 1,10-phenanthroline-based (A-D-A-D-A) and oligothiophene-based (A-D-D-D-(D)-A) heterocyclic aromatic fluorescence compounds having N-containing imidazole and pyridine tails with effective π-conjugated systems, prepared by the combination of carbon-carbon (C-C) bond and carbon-nitrogen (C-N) bond cross-coupling reactions, is described. They have molecular lengths of more than 2.30 nm in the cases of 4, 6, 9, and 26, various D-A spacers, and certain N-coordination sites (phen, imidazole, and pyridine). X-ray single-crystal structures of 13 compounds reveal a variety of trans and cis configurations with different dihedral angles between adjacent aromatic heterocycles. Synthetic, computational, and spectral studies have been made to reveal the differences between cross-coupling approaches on the C-C bond and C-N bond formation as well as band gaps and energy levels and optical and electrochemical properties for related compounds. The influences of introducing a β-methyl group to the thiophene ring on reaction activity, solubility, and conformation of related compounds have also been discussed. PMID:21513323

The platinum(IV) complexes fac-L(2)PtMe(3)(OR) (L(2) = bis(diphenylphosphino)ethane, o-bis(diphenylphosphino)benzene, R = carboxyl, aryl; L = PMe(3), R = aryl) undergo reductive elimination reactions to form carbon-oxygen bonds and/or carbon-carbonbonds. The carbon-oxygen reductive elimination reaction produces either methyl esters or methyl aryl ethers (anisoles) and L(2)PtMe(2), while the carbon-carbon reductive elimination reaction affords ethane and L(2)PtMe(OR). Choice of reaction conditions allows the selection of either type of coupling over the other. A detailed mechanistic study of the reductive elimination reactions supports dissociation of the OR(-) ligand as the initial step for the C-O bond formation reaction. This is followed by a nucleophilic attack of OR(-) upon a methyl group bound to the Pt(IV) cation to produce the products MeOR and L(2)PtMe(2). C-C reductive elimination proceeds from L(2)PtMe(3)(OR) by initial L (L = PMe(3)) or OR(-) (L(2) = dppe, dppbz) dissociation, followed by C-C coupling from the resulting five-coordinate intermediate. Our studies demonstrate that both C-C and C-O reductive elimination reactions from Pt(IV) are more facile in polar solvents, in the presence of Lewis acids, and for OR(-) groups that contain electron withdrawing substituents. PMID:11456927

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[reaction: see text] [cis-Ru(II)(dmp)2(H2O)2]2+ (dmp = 2,9-dimethylphenanthroline) was found to be a selective oxidation catalyst using hydrogen peroxide as oxidant. Thus, primary alkenes were very efficiently oxidized via direct carbon-carbonbond cleavage to the corresponding aldehydes as an alternative to ozonolysis. Secondary alkenes were much less reactive, leading to regioselective oxidation of substrates such as 4-vinylcyclohexene and 7-methyl-1,6-octadiene at the terminal position. Primary allylic alcohols were chemoselectively oxidized to the corresponding allylic aldehydes, e.g., geraniol to citral. PMID:16235952

The enzyme 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) lyase catalyzes the terminal steps in ketone body generation and leucine degradation. Mutations in this enzyme cause a human autosomal recessive disorder called primary metabolic aciduria, which typically kills victims because of an inability to tolerate hypoglycemia. Here we present crystal structures of the HMG-CoA lyases from Bacillus subtilis and Brucella melitensis at 2.7 and 2.3 {angstrom} resolution, respectively. These enzymes share greater than 45% sequence identity with the human orthologue. Although the enzyme has the anticipated triose-phosphate isomerase (TIM) barrel fold, the catalytic center contains a divalent cation-binding site formed by a cluster of invariant residues that cap the core of the barrel, contrary to the predictions of homology models. Surprisingly, the residues forming this cation-binding site and most of their interaction partners are shared with three other TIM barrel enzymes that catalyze diverse carbon-carbonbond cleavage reactions believed to proceed through enolate intermediates (4-hydroxy-2-ketovalerate aldolase, 2-isopropylmalate synthase, and transcarboxylase 5S). We propose the name 'DRE-TIM metallolyases' for this newly identified enzyme family likely to employ a common catalytic reaction mechanism involving an invariant Asp-Arg-Glu (DRE) triplet. The Asp ligates the divalent cation, while the Arg probably stabilizes charge accumulation in the enolate intermediate, and the Glu maintains the precise structural alignment of the Asp and Arg. We propose a detailed model for the catalytic reaction mechanism of HMG-CoA lyase based on the examination of previously reported product complexes of other DRE-TIM metallolyases and induced fit substrate docking studies conducted using the crystal structure of human HMG-CoA lyase (reported in the accompanying paper by Fu, et al. (2006) J. Biol. Chem. 281, 7526-7532). Our model is consistent with extensive mutagenesis results and

A biogenetic type total synthesis of alkaloids phaitanthrin D and phaitanthrin E has been described. The Csp(3)-Csp(3) bond cleavage with the release of several heteroatoms bearing unexpected leaving groups in intramolecular substitution reactions on an iminium double bond in the quinazolinones has been demonstrated using HMDS/ZnCl2 or NaHMDS. The mechanistic aspects have been supported by isolation and characterization of appropriate intermediates. PMID:26650567

Addition of two Ln-H bonds of an Yb(II) hydrido complex supported by bulky amidinate ligand to a C≡C bond lead to the formation of 1,2-dianionic bibenzyl fragment. Both Yb(II) and hydrido centers are oxidized under the reaction conditions. The resulting Yb(II)-η(6) -arene interaction is surprisingly robust: the arene cannot be replaced from the metal coordination sphere when treated with Lewis bases. PMID:22374856

An improved structure for carbon-carbon composite piston architectures consists of replacing the knitted fiber, three-dimensional piston preform architecture described in U.S. Pat. No. 4.909,133 (Taylor et al.) with a two-dimensional lay-up or molding of carbon fiber fabric or tape. Initially. the carbon fabric or tape layers are prepregged with carbonaceous organic resins and/or pitches and are laid up or molded about a mandrel. to form a carbon-fiber reinforced organic-matrix composite part shaped like a "U" channel, a "T"-bar. or a combination of the two. The molded carbon-fiber reinforced organic-matrix composite part is then pyrolized in an inert atmosphere, to convert the organic matrix materials to carbon. At this point, cylindrical piston blanks are cored from the "U" channel, "T"-bar, or combination part. These blanks are then densified by reimpregnation with resins or pitches which are subsequently carbonized. Densification is also be accomplished by direct infiltration with carbon by vapor deposition processes. Once the desired density has been achieved, the piston billets are machined to final piston dimensions; coated with oxidation sealants; and/or coated with a catalyst. When compared to conventional steel or aluminum-alloy pistons, the use of carbon-carbon composite pistons reduces the overall weight of the engine; allows for operation at higher temperatures without a loss of strength; allows for quieter operation; reduces the heat loss; and reduces the level of hydrocarbon emissions.

A lightweight cylinder block composed of carbon-carbon is disclosed. The use of carbon-carbon over conventional materials, such as cast iron or aluminum, reduces the weight of the cylinder block and improves thermal efficiency of the internal combustion reciprocating engine. Due to the negligible coefficient of thermal expansion and unique strength at elevated temperatures of carbon-carbon, the piston-to-cylinder wall clearance can be small, especially when the carbon-carbon cylinder block is used in conjunction with a carbon-carbon piston. Use of the carbon-carbon cylinder block has the effect of reducing the weight of other reciprocating engine components allowing the piston to run at higher speeds and improving specific engine performance.

Carbon-Carbon (C-C) Radiator was a success and proved that the technology can work to reduce Spacecraft weight. C-C has a niche, especially for high temperatures. C-C still needs further development: reduction in fabrication time and cost - high conductivity "traditional" composites are more competitive, and CTE interface issues with heat pipes. Redundancy a good idea - we flew the spare panel. CSRP was a success -informal inter-agency partnership. Possible follow-on: C-C foam for low CTE mirrors/optical benches.

Considers carbon-carbon multiple bonds in terms of Pauling's bent bond model, which allows direct calculation of double and triple bonds from the length of a CC single bond. Lengths of these multiple bonds are estimated from direct measurements on "bent-bond" models constructed of plastic tubing and standard kits. (CS)

...) Individual bond. Covers a named individual in a stated penalty. (b) Name schedule bond. Covers a number of... 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-10 Individual or schedule or blanket form of bonds. Section 13 provides that “any bond shall be in a form or of a type approved by...

A new piston concept, made of carbon-carbon refractory-composite material, has been developed that overcomes a number of the shortcomings of aluminum pistons. Carbon-carbon material, developed in the early 1960's, is lighter in weight than aluminum, has higher strength and stiffness than aluminum and maintains these properties at temperatures over 2500 F. In addition, carbon-carbon material has a low coefficient of thermal expansion and excellent resistance to thermal shock. An effort, called the Advanced Carbon-Carbon Piston Program was started in 1986 to develop and test carbon-carbon pistons for use in spark ignition engines. The carbon-carbon pistons were designed to be replacements for existing aluminum pistons, using standard piston pin assemblies and using standard rings. Carbon-carbon pistons can potentially enable engines to be more reliable, more efficient and have greater power output. By utilizing the unique characteristics of carbon-carbon material a piston can: (1) have greater resistance to structural damage caused by overheating, lean air-fuel mixture conditions and detonation; (2) be designed to be lighter than an aluminum piston thus, reducing the reciprocating mass of an engine, and (3) be operated in a higher combustion temperature environment without failure.

An improved structure for carbon-carbon composite piston architectures is disclosed. The improvement consists of replacing the knitted fiber, three-dimensional piston preform architecture described in U.S. Pat.No. 4,909,133 (Taylor et al.) with a two-dimensional lay-up or molding of carbon fiber fabric or tape. Initially, the carbon fabric of tape layers are prepregged with carbonaceous organic resins and/or pitches and are laid up or molded about a mandrel, to form a carbon-fiber reinforced organic-matrix composite part shaped like a "U" channel, a "T"-bar, or a combination of the two. The molded carbon-fiber reinforced organic-matrix composite part is then pyrolized in an inert atmosphere, to convert the organic matrix materials to carbon. At this point, cylindrical piston blanks are cored from the "U"-channel, "T"-bar, or combination part. These blanks are then densified by reimpregnation with resins or pitches which are subsequently carbonized. Densification is also accomplished by direct infiltration with carbon by vapor deposition processes. Once the desired density has been achieved, the piston billets are machined to final piston dimensions; coated with oxidation sealants; and/or coated with a catalyst. When compared to conventional steel or aluminum alloy pistons, the use of carbon-carbon composite pistons reduces the overall weight of the engine; allows for operation at higher temperatures without a loss of strength; allows for quieter operation; reduces the heat loss; and reduces the level of hydrocarbon emissions.

We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2](-) may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride. PMID:26491957

The microstructure and strength of Mo/mullite interfaces formed by diffusion bonding at 1650 C has been analyzed. Interfacial metal-ceramic interlocking contributes to flexural strength of approx. 140 MPa as measured by 3 point bending. Saturation of mullite with MoO2 does not affect the interfacial strength.

Disulfide bonds are important for the stability and function of many secreted proteins. In Gram-negative bacteria, these linkages are catalyzed by thiol-disulfide oxidoreductases (Dsb) in the periplasm. Protein oxidation has been well studied in these organisms, but it has not fully been explored in Gram-positive bacteria, which lack traditional periplasmic compartments. Recent bioinformatics analyses have suggested that the high-GC-content bacteria (i.e., actinobacteria) rely on disulfide-bond-forming pathways. In support of this, Dsb-like proteins have been identified in Mycobacterium tuberculosis, but their functions are not known. Actinomyces oris and Corynebacterium diphtheriae have recently emerged as models to study disulfide bond formation in actinobacteria. In both organisms, disulfide bonds are catalyzed by the membrane-bound oxidoreductase MdbA. Remarkably, unlike known Dsb proteins, MdbA is important for pathogenesis and growth, which makes it a potential target for new antibacterial drugs. This review will discuss disulfide-bond-forming pathways in bacteria, with a special focus on Gram-positive bacteria. PMID:26644434

This paper presents results from material performance evaluations of oxidation-resistant carbon-carbon composites intended for multiuse aerospace applications, which cover the effects of the following environmental parameters: the oxidizing nature of the environments (including both high and low oxygen partial pressures), high temperatures, moisture, cyclic temperature service, and foreign-object impact. Results are presented for the carbon-carbon material currently in use as the thermal-protection-system material on Space Shuttle, as well as for newer and more advanced structural forms of carbon-carbon composites.

A method of forming a virtual substrate comprised of an optoelectronic device substrate and handle substrate comprises the steps of initiating bonding of the device substrate to the handle substrate, improving or increasing the mechanical strength of the device and handle substrates, and thinning the device substrate to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. The handle substrate is typically Si or other inexpensive common substrate material, while the optoelectronic device substrate is formed of more expensive and specialized electro-optic material. Using the methodology of the invention a wide variety of thin film electro-optic materials of high quality can be bonded to inexpensive substrates which serve as the mechanical support for an optoelectronic device layer fabricated in the thin film electro-optic material.

A method of forming a virtual substrate comprised of an optoelectronic device substrate and handle substrate comprises the steps of initiating bonding of the device substrate to the handle substrate, improving or increasing the mechanical strength of the device and handle substrates, and thinning the device substrate to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. The handle substrate is typically Si or other inexpensive common substrate material, while the optoelectronic device substrate is formed of more expensive and specialized electro-optic material. Using the methodology of the invention a wide variety of thin film electro-optic materials of high quality can be bonded to inexpensive substrates which serve as the mechanical support for an optoelectronic device layer fabricated in the thin film electro-optic material.

The general plane strain problem of adhesively bonded structures consisting of two different, orthotropic adherends is considered, under the assumption that adherend thicknesses are constant and small in relation to the lateral dimensions of the bonded region, so that they may be treated as plates. The problem is reduced to a system of differential equations for the adhesive stresses which is solved in closed form, with a single lap joint and a stiffened plate under various loading conditions being considered as examples. It is found that the plate theory used in the analysis not only predicts the correct trend for adhesive stresses but gives surprisingly accurate results, the solution being obtained by assuming linear stress-strain relations for the adhesive.

... of Termination of Bond. When the appropriate TTB officer is satisfied that any bond given under the provisions of this subpart may be terminated, he shall issue Form 1490, Notice of Termination of Bond,...

... of Termination of Bond. When the appropriate TTB officer is satisfied that any bond given under the provisions of this subpart may be terminated, he shall issue Form 1490, Notice of Termination of Bond,...

Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. We have developed a magnesium phosphate ceramic to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests.

... 27 Alcohol, Tobacco Products and Firearms 2 2012-04-01 2011-04-01 true Form of bond and security... Collection of Excise and Special (Occupational) Tax Bonds § 70.281 Form of bond and security required. (a) In general. Any person required to furnish a bond under the provisions of this part shall execute such...

... 27 Alcohol, Tobacco Products and Firearms 2 2014-04-01 2014-04-01 false Form of bond and security... Collection of Excise and Special (Occupational) Tax Bonds § 70.281 Form of bond and security required. (a) In general. Any person required to furnish a bond under the provisions of this part shall execute such...

... 27 Alcohol, Tobacco Products and Firearms 2 2013-04-01 2013-04-01 false Form of bond and security... Collection of Excise and Special (Occupational) Tax Bonds § 70.281 Form of bond and security required. (a) In general. Any person required to furnish a bond under the provisions of this part shall execute such...

... 12 Banks and Banking 5 2010-01-01 2010-01-01 false Bonds for directors, officers, employees, and agents; form of and amount of bonds. 563.190 Section 563.190 Banks and Banking OFFICE OF THRIFT... provided by the insurance underwriter industry's standard forms, through the use of endorsements,...

... ADMINISTRATION, DEPARTMENT OF LABOR TEMPORARY BONDING RULES UNDER THE EMPLOYEE RETIREMENT INCOME SECURITY ACT OF 1974 TEMPORARY BONDING RULES Scope and Form of the Bond § 2580.412-10 Individual or schedule or blanket.... Bonding, to the extent required, of persons indirectly employed, or otherwise delegated, to...

... 25 Indians 1 2011-04-01 2011-04-01 false What form of bonds will the BIA accept? 166.602 Section 166.602 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR LAND AND WATER GRAZING PERMITS Bonding and Insurance Requirements § 166.602 What form of bonds will the BIA accept? (a) We will...

A document summarizes the development of a carbon-carbon composite radiator for dissipating waste heat from a spacecraft nuclear reactor. The radiator is to be bonded to metal heat pipes and to operate in conjunction with them at a temperature approximately between 500 and 1,000 K. A goal of this development is to reduce the average areal mass density of a radiator to about 2 kg/m(exp 2) from the current value of approximately 10 kg/m(exp 2) characteristic of spacecraft radiators made largely of metals. Accomplishments thus far include: (1) bonding of metal tubes to carbon-carbon material by a carbonization process that includes heating to a temperature of 620 C; (2) verification of the thermal and mechanical integrity of the bonds through pressure-cycling, axial-shear, and bending tests; and (3) construction and testing of two prototype heat-pipe/carbon-carbon-radiator units having different radiator areas, numbers of heat pipes, and areal mass densities. On the basis of the results achieved thus far, it is estimated that optimization of design could yield an areal mass density of 2.2 kg/m (exp 2) close to the goal of 2 kg/m(exp 2).

... Shipping MARITIME ADMINISTRATION, DEPARTMENT OF TRANSPORTATION EMERGENCY OPERATIONS WAR RISK INSURANCE War Risk Cargo Insurance Ii-Open Policy War Risk Cargo Insurance § 308.528 Surety Bond A, Form MA-308. The Standard Form of Surety Bond A, Form MA-308, which may be obtained from the American War Risk Agency...

A process for making 2D and 3D carbon-carbon composites having a combined high crystallinity, high strength, high modulus and high thermal and electrical conductivity. High-modulus/high-strength mesophase derived carbon fibers are woven into a suitable cloth. Layers of this easily graphitizible woven cloth are infiltrated with carbon material to form green composites. The carbonized composite is then impregnated several times with pitch by covering the composite with hot pitch under pressure. The composites are given a heat treatment between each impregnant step to crack up the infiltrated carbon and allow additional pitch to enter the microstructure during the next impregnation cycle. The impregnated composites are then given a final heat treatment in the range 2500.degree. to 3100.degree. C. to fully graphitize the fibers and the matrix carbon. The composites are then infiltrated with pyrolytic carbon by chemical vapor deposition in the range 1000.degree. C. to 1300.degree. C. at a reduced. pressure.

Many of the properties of carbon-carbon make it an ideal material for reciprocating materials of intermittent combustion (IC) engines. Recent diesel engine tests, shown herein, indicate that the thermal and mechanical properties of carbon-carbon are adequate for piston applications, However, reducing the manufacturing costs and providing long term oxidation protection are still issues that need to be addressed.

The series of bis(eta/sup 2/-iminoacyl) compounds of general formula M(OAr)/sub 2/(eta/sup 2/-R'NCR)/sub 2/ (M = Ti, Zr, Hf; OAr = 2,6-diisopropyl- and 2,6-di-tert-butylphenoxide; R = CH/sub 3/, CH/sub 2/Ph; R' = various substituted phenyls) undergo intramolecular coupling on thermolysis to produce the corresponding enediamide derivatives M(OAr)/sub 2/(R'NC(R) = C(R)NR'). A kinetic study of the reaction in hydrocarbon solvents has shown it to be first order. The reaction is metal dependent with the rate decreasing in the order Ti > Zr > Hf. The rate of the reaction is also dependent on the steric and electronic nature of the nitrogen substituent (R'). The use of the bulky aryl group 2,6-dimethylphenyl retards the reaction, while the use of various 3- and 4-substituted phenyls (3-F, 3-OMe, 4-OMe, 4-Cl, 4-NMe/sub 2/) shows the reaction to be accelerated by electron-withdrawing substituents. A sigma plot based on kinetic data obtained at 67/sup 0/C and 77/sup 0/C yielded rho values of 0.83 (R = 0.97) and 0.84 (R = 0.95), respectively. Both the steric and electronic dependence of the reactivity on the nitrogen substituents is discussed mechanistically and used to rationalize the much more facile intramolecular coupling observed for the related eta/sup 2/-acyl (eta/sup 2/-OCR) functionalities.

Abstract

Unlike heterodimerization reactions of ethylene and vinylarenes, no such synthetically useful reactions using propylene are known. We find that propylene reacts with various vinylarenes in the presence of catalytic amounts of [(allyl)NiBr]2, triphen...

A method of densifying an article formed of reaction bonded silicon nitride is disclosed. The reaction bonded silicon nitride article is packed in a packing mixture consisting of silicon nitride powder and a densification aid. The reaction bonded silicon nitride article and packing powder are sujected to a positive, low pressure nitrogen gas treatment while being heated to a treatment temperature and for a treatment time to cause any open porosity originally found in the reaction bonded silicon nitride article to be substantially closed. Thereafter, the reaction bonded silicon nitride article and packing powder are subjected to a positive high pressure nitrogen gas treatment while being heated to a treatment temperature and for a treatment time to cause a sintering of the reaction bonded silicon nitride article whereby the strength of the reaction bonded silicon nitride article is increased.

We present a novel ultraviolet (UV)-curable mold that enables the formation of reversibly bonded nanocapillaries (500-50 nm) on a gold or silicon substrate. A sheet-type ( approximately 50 microm) polyethylene diacrylate (PEG-DA) mold was used for its rigiflex nature; it provides rigidity high enough for maintaining nanostructures (elastic modulus >70 MPa) and also flexibility good enough for intimate contact over a large area aided by weak electrostatic forces (zeta potential approximately -113.55 mW). The electrostatic charge is generated on a rigiflex PEG-DA mold upon peeling from an original engraved silicon master by mechanical friction, thereby assisting the formation of spontaneous contact with the gold or silicon substrate. PMID:17343400

The mechanism by which urea and guanidinium destabilize protein structure is controversial. We tested the possibility that these denaturants form hydrogen bonds with peptide groups by measuring their ability to block acid- and base-catalyzed peptide hydrogen exchange. The peptide hydrogen bonding found appears sufficient to explain the thermodynamic denaturing effect of urea. Results for guanidinium, however, are contrary to the expectation that it might H-bond. Evidently, urea and guanidinium, although structurally similar, denature proteins by different mechanisms. PMID:19196963

An improved structure for a reciprocating internal combustion engine or compressor piston fabricate from carbon-carbon composite materials is disclosed. An integral ring carbon-carbon composite piston, disclosed herein, reduces the need for piston rings and for small clearances by providing a small flexible, integral component around the piston that allows for variation in clearance due to manufacturing tolerances, distortion due to pressure and thermal loads, and variations in thermal expansion differences between the piston and cylinder liner.

Curdlan and other beta-1,3-D-glucans form right-handed triple helices, and it has been believed that the intermolecular H-bond is present at the center of the helix to maintain the structure. In this H-bond model, three secondary OH groups form an inequilateral hexagonal shape perpendicular to the helix axis. This hexagonal form seems to be characteristic for beta-1,3-D-glucans and is widely accepted. We carried out MOPAC and ab initio calculations for the curdlan helix, and we propose a new intermolecular H-bonding model. In our model, the H-bonds are formed between the O2-atoms on different x-y planes along the curdlan helix, hence the H-bonds are not perpendicular to the helix axis. The new H-bonds are connected along the helix, traversing three curdlan chains to make a left-handed helix. Therefore, the H-bonding array leads to a reverse helix of the main chain. According to our MOPAC calculation, this model is more stable than the previous one. We believe that the continuous H-bonding array is stabilized by cooperative phenomena in the polymeric system. PMID:17191891

The cleanup activities of the Hanford tank wastes require stabilization and solidification of the secondary waste streams generated from the processing of the tank wastes. The treatment of these tank wastes to produce glass waste forms will generate secondary wastes, including routine solid wastes and liquid process effluents. Liquid wastes may include process condensates and scrubber/off-gas treatment liquids from the thermal waste treatment. The current baseline for solidification of the secondary wastes is a cement-based waste form. However, alternative secondary waste forms are being considered. In this regard, Ceramicrete technology, developed at Argonne National Laboratory, is being explored as an option to solidify and stabilize the secondary wastes. The Ceramicrete process has been demonstrated on four secondary waste formulations: baseline, cluster 1, cluster 2, and mixed waste streams. Based on the recipes provided by Pacific Northwest National Laboratory, the four waste simulants were prepared in-house. Waste forms were fabricated with three filler materials: Class C fly ash, CaSiO{sub 3}, and Class C fly ash + slag. Optimum waste loadings were as high as 20 wt.% for the fly ash and CaSiO{sub 3}, and 15 wt.% for fly ash + slag filler. Waste forms for physical characterizations were fabricated with no additives, hazardous contaminants, and radionuclide surrogates. Physical property characterizations (density, compressive strength, and 90-day water immersion test) showed that the waste forms were stable and durable. Compressive strengths were >2,500 psi, and the strengths remained high after the 90-day water immersion test. Fly ash and CaSiO{sub 3} filler waste forms appeared to be superior to the waste forms with fly ash + slag as a filler. Waste form weight loss was {approx}5-14 wt.% over the 90-day immersion test. The majority of the weight loss occurred during the initial phase of the immersion test, indicative of washing off of residual unreacted

The effects of substitution on the direct /sup 13/C-/sup 13/C spin-spin coupling constants of the triple bond were studied in 100 derivatives of acetylene. It was established that these parameters exhibit increased sensitivity to the effect of substituents compared with other types of compounds. The main factor which determines their variation is the electronegativity of the substituting groups, and in individual cases the /pi/-electronic effects are appreciable. The effect of the substituents with an element of the silicon subgroup at the /alpha/ position simultaneously at the triple bond or substituent of the above-mentioned type and a halogen atom.

An emerging class of high temperature materials called carbon-carbon composites are being developed to help make advanced aerospace flight become a reality. Because of the high temperature strength and low density of carbon-carbon composites, aerospace engineers would like to use these materials in even more advanced applications. One application of considerable interest is as the structure of the aerospace vehicle itself rather than simply as a protective heat shield as on Space Shuttle. But suitable forms of these materials have yet to be developed. If this development can be successfully accomplished, advanced aerospace vehicles such as the National Aero-Space Plane (NASP) and other hypersonic vehicles will be closer to becoming a reality. A brief definition is given of C-C composites. Fabrication problems and oxidation protection concepts are examined. Applications of C-C composites in the Space Shuttle and in advanced hypersonic vehicles as well as other applications are briefly discussed.

Low-temperature Cu–Cu direct bonding becomes of great importance as Cu is widely used as an interconnection material in the packaging industry. Preparing a clean surface is a key to successful Cu–Cu direct bonding. We investigated the effects of forming gas plasma treatment on the reduction of Cu oxide and Cu–Cu bonding temperature. As plasma input power and treatment time increased, Cu oxide could be effectively reduced, and this could be attributed to the enhanced chemical reaction between forming gas plasma and Cu oxide. When the bonding temperature was reduced from 415 to 300 °C, the bonding strength of the plasma-treated interface was increased from 1.8 to 5.55 J/m2 while that of the wet-treated interface was decreased.

The procedure to estimate the carbon-carbonbond distance in the naphthalene molecule is described. The procedure is easily performed and can be done either at home or in the classroom, with the restriction that the mass of the naphthalene must be determined using an analytical or a precise balance.

We perform dispersion-corrected first-principles calculations, and far-infrared (terahertz) spectroscopic experiments at 4 K, to examine translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I. The calculated frequencies and relative intensities reproduce the observed spectrum to accuracy of 11 cm-1 or less. The stronger one of the two peaks assigned to the translational mode includes the stretching vibration of the weak hydrogen bond between the acetyl groups of a neighboring one-dimensional chain. The calculation of aspirin form II performed for comparison gives the stretching vibration of the weak hydrogen bond in one-dimensional chain.

A process for making a carbon-carbon composite having a combination of high crystallinity, high strength, high modulus and high thermal and electrical conductivity. High-modulus/high-strength mesophase derived carbon fibers are woven into a suitable cloth. Layers of this easily graphitizable woven cloth are covered with petroleum or coal tar pitch and pressed at a temperature a few degrees above the softening point of the pitch to form a green laminated composite. The green composite is restrained in a suitable fixture and heated slowly to carbonize the pitch binder. The carbonized composite is then impregnated several times with pitch by covering the composite with hot pitch under pressure. The composites are given a heat treatment between each impregnation step to crack up the infiltrated carbon and allow additional pitch to enter the microstructure during the next impregnation cycle. The impregnated composites are then given a final heat treatment in the range 2500.degree. to 3000.degree. C. to fully graphitize the fibers and the matrix carbon. The composites are then infiltrated with pyrolytic carbon by chemical vapor deposition in the range 1000.degree. to 1300.degree. C. at a reduced pressure for approximately one hundred and fifty (150) hours.

... savings bonds only in book-entry form? 351.83 Section 351.83 Money and Finance: Treasury Regulations... Debt issue Series EE savings bonds only in book-entry form? We reserve the right to issue bonds only in book-entry form....

Significant advancements have been made in the development of lightweight, high performance, carbon-carbon heat pipes for space nuclear power applications. The subject program has progressed through the concept definition and feasibility analysis stages to the current test article component fabrication and assembly phase. This concept utilizes a carbon-carbon tube with integrally woven fins as the primary structural element and radiative surface, Nb-1Zr liners to contain a potassium working fluid, and welded end caps and fill tubes. Various tests have been performed in the development of suitable liner bonding techniques and in the assessment of material stability.

Significant advancements have been made in the development of lightweight, high performance, carbon-carbon heat pipes for space nuclear power applications. The subject program has progressed through the concept definition and feasibility analysis stages to the current test article component fabrication and assembly phase. This concept utilizes a carbon-carbon tube with integrally woven fins as the primary structural element and radiative surface, Nb-1Zr liners to contain a potassium working fluid, and welded end caps and fill tubes. Various tests have been performed in the development of suitable liner bonding techniques and in the assessment of material stability.

... 46 CFR part 515 and 520, and pursuant to section 19 of the 1984 Act, files this bond with the... available to pay any judgment or any settlement made pursuant to a claim under 46 CFR § 515.23(b) for... settlement made pursuant to a claim under 46 CFR § 515.23(b) for damages against the Principal arising...

... 46 CFR part 515 and 520, and pursuant to section 19 of the 1984 Act, files this bond with the... available to pay any judgment or any settlement made pursuant to a claim under 46 CFR § 515.23(b) for... settlement made pursuant to a claim under 46 CFR § 515.23(b) for damages against the Principal arising...

... 46 CFR part 515 and 520, and pursuant to section 19 of the 1984 Act, files this bond with the... available to pay any judgment or any settlement made pursuant to a claim under 46 CFR § 515.23(b) for... settlement made pursuant to a claim under 46 CFR § 515.23(b) for damages against the Principal arising...

Na-doped hydroxyapatite (Na-HA) coating was directly prepared onto carbon/carbon (C/C) composites using electrochemical deposition (ECD) and the mean thickness of the coating is approximately 10 ± 2 μm. The formed Na-HA crystals which are Ca-deficient, are rod-like with a hexagonal cross section. The Na/P molar ratios of the coating formed on C/C substrate is 0.097. During the deposition, the Na-HA crystals grow in both radial and longitudinal directions, and faster along the longitudinal direction. The pattern formation of crystal growth leads to dense coating which would help to increase the bonding strength of the coating. The average shear bonding strength of Na-HA coating on C/C is 5.55 ± 0.77 MPa. The in vitro bioactivity of the Na-HA coated C/C composites were investigated by soaking the samples in a simulated body fluid (SBF) for 14 days. The results indicate that the Na-HA coated C/C composites can rapidly induce bone-like apatite nucleation and growth on its surface in SBF. The in vitro cellular biocompatibility tests reveal that the Na-HA coating was better to improve the in vitro biocompatibility of C/C composites compared with hydroxyapatite (HA) coating. It was suggested that the Na-HA coating might be an effective method to improve the surface bioactivity and biocompatibility of C/C composites.

The plethora of ice structures observed both in bulk and under nanoscale confinement reflects the extraordinary ability of water molecules to form diverse forms of hydrogen bonding networks. An ideal hydrogen bonding network of water should satisfy three requirements: (1) four hydrogen bonds connected with every water molecule, (2) nearly linear hydrogen bonds, and (3) tetrahedral configuration for the four hydrogen bonds around an O atom. However, under nanoscale confinement, some of the three requirements have to be unmet, and the selection of the specific requirement(s) leads to different types of hydrogen bonding structures. According to molecular dynamics (MD) simulations for water confined between two smooth hydrophobic walls, we obtain a phase diagram of three two-dimensional (2D) crystalline structures and a bilayer liquid. A new 2D bilayer ice is found and named the interlocked pentagonal bilayer ice (IPBI), because its side view comprises interlocked pentagonal channels. The basic motif in the top view of IPBI is a large hexagon composed of four small pentagons, resembling the top view of a previously reported "coffin" bilayer ice [Johnston, et al., J. Chem. Phys., 2010, 133, 154516]. First-principles optimizations suggest that both bilayer ices are stable. However, there are fundamental differences between the two bilayer structures due to the difference in the selection among the three requirements. The IPBI sacrifices the linearity of hydrogen bonds to retain locally tetrahedral configurations of the hydrogen bonds, whereas the coffin structure does the opposite. The tradeoff between the conditions of an ideal hydrogen bonding network can serve as a generic guidance to understand the rich phase behaviors of nanoconfined water. PMID:27063210

... 31 Money and Finance:Treasury 2 2011-07-01 2011-07-01 false May Public Debt issue Series I savings bonds only in book-entry form? 359.68 Section 359.68 Money and Finance: Treasury Regulations Relating to... Series I savings bonds only in book-entry form? We reserve the right to issue bonds only in...

... 31 Money and Finance: Treasury 2 2010-07-01 2010-07-01 false May Public Debt issue Series I savings bonds only in book-entry form? 359.68 Section 359.68 Money and Finance: Treasury Regulations... Debt issue Series I savings bonds only in book-entry form? We reserve the right to issue bonds only...

Weak noncovalent intermolecular interactions play a pivotal role in many biological processes such as cell adhesion or immunology, where the overall binding strength is controlled through bond association and dissociation dynamics as well as the cooperative action of many parallel bonds. Among the various molecules participating in weak bonds, carbohydrate-carbohydrate interactions are probably the most ancient ones allowing individual cells to reversibly enter the multicellular state and to tell apart self and nonself cells. Here, we scrutinized the kinetics and thermodynamics of small homomeric Lewis X-Lewis X ensembles formed in the contact zone of a membrane-coated colloidal probe and a solid supported membrane ensuring minimal nonspecific background interactions. We used an atomic force microscope to measure force distance curves at Piconewton resolution, which allowed us to measure the force due to unbinding of the colloidal probe and the planar membrane as a function of contact time. Applying a contact model, we could estimate the free binding energy of the formed adhesion cluster as a function of dwell time and thereby determine the precise size of the contact zone, the number of participating bonds, and the intrinsic rates of association and dissociation in the presence of calcium ions. The unbinding energy per bond was found to be on the order of 1 kBT. Approximately 30 bonds were opened simultaneously at an off-rate of koff = 7 ± 0.2 s(-1). PMID:27074683

Time-of-flight mass spectrometry reveals that atomic and small molecular triply charged cations exhibit extensive bond-forming chemistry, following gas-phase collisions with neutral molecules. These experiments show that at collision energies of a few eV, I(3+) reacts with a variety of small molecules to generate molecular monocations and molecular dications containing iodine. Xe(3+) and CS2(3+) react in a similar manner to I(3+), undergoing bond-forming reactions with neutrals. A simple model, involving relative product energetics and electrostatic interaction potentials, is used to account for the observed reactivity. PMID:23843367

A glass-bonded ceramic waste form is being developed to immobilize high-level chloride waste salts generated during the conditioning of spent sodium-bonded nuclear fuel for disposal. The waste salt is loaded into zeolite cavities, mixed with a borosilicate glass, and consolidated at 800--900 C by hot isostatic pressing. During this process, small amounts of halite are generated, whereas the zeolite converts to the mineral sodalite, which retains most of the waste salt. In this work, optical microscopy, scanning electron microscopy, and transmission electron microscopy2048e used to characterize the halite inclusions in the final waste form. The halite inclusions were detected within micron- to submicron-sized pores that form within the glass phase in the vicinity of the sodalite/glass interface. The chemical nature and distribution of the halite inclusions were determined. The particular microstructure of the halite inclusions has been related to the corrosion of the ceramic waste form.

This project was focused upon developing a unique material technology for use in PEM fuel cell bipolar plates. The carbon/carbon composite material developed in this program is uniquely suited for use in fuel cell systems, as it is lightweight, highly conductive and corrosion resistant. The project further focused upon developing the manufacturing methodology to cost-effectively produce this material for use in commercial fuel cell systems. United Technology Fuel Cells Corp., a leading fuel cell developer was a subcontractor to the project was interested in the performance and low-cost potential of the material. The accomplishments of the program included the development and testing of a low-cost, fully molded, net-shape carbon-carbon bipolar plate. The process to cost-effectively manufacture these carbon-carbon bipolar plates was focused on extensively in this program. Key areas for cost-reduction that received attention in this program was net-shape molding of the detailed flow structures according to end-user design. Correlations between feature detail and process parameters were formed so that mold tooling could be accurately designed to meet a variety of flow field dimensions. A cost model was developed that predicted the cost of manufacture for the product in near-term volumes and long-term volumes (10+ million units per year). Because the roduct uses lowcost raw materials in quantities that are less than competitive tech, it was found that the cost of the product in high volume can be less than with other plate echnologies, and can meet the DOE goal of $4/kW for transportation applications. The excellent performance of the all-carbon plate in net shape was verified in fuel cell testing. Performance equivalent to much higher cost, fully machined graphite plates was found.

Upgrading furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbonbonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbonbond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan can be coupled with various C1 to C4 low molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase to produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (∼25 kcal/mol) are lower than the cellulose activation or decomposition reactions (∼50 kcal/mol). Cycloaddition of C5-C8 cyclo ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products, and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ∼20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons. PMID:24902118

Carbon/Carbon Composites (CCC) are made of carbon reinforcement in carbon matrix and have high thermal stability and fatigue resistance. CCC are used in nose cones, heat shields and disc brakes of aircrafts due to their exceptional mechanical properties at high temperature. The manufacturing process of CCC involves a carbonization stage in which unwanted elements, except carbon, are eliminated from the polymer precursor. Carbonization results in the formation of voids and cracks due to the thermal mismatch between the reinforcement and the matrix and expulsion of volatiles from the polymer matrix. Thermal cracks and voids decrease the density and mechanical properties of the manufactured CCC. In this work, Nanographene Platelets (NGP) were explored as nanofillers to fill the voids/cracks and reduce thermal shrinkage in CCC. They were first compared with Vapor Grown Carbon Nanofibers (VGCNF) by dispersion of different concentrations (0.5wt%, 1.5wt%, 3wt%) in resole-type phenolic resin and were characterized to explore their effect on rheology, heat of reaction and wetting behavior. The dispersions were then cured to form nanocomposites and were characterized for morphology, flexure and thermal properties. Finally, NGP were introduced into the carbon/carboncomposites in two stages, first by spraying in different concentrations (0.5wt%, 1.5wt%, 3wt%, 5wt %) during the prepreg formation and later during densification by directly mixing in the corresponding densification mix. The manufactured NGP reinforced CCC were characterized for microstructure, porosity, bulk density and mechanical properties (Flexure and ILSS) which were further cross-checked by non-destructive techniques (vibration and ultrasonic). In this study, it was further found that at low concentration (≤ 1.5 wt%) NGP were more effective in increasing the heat of reaction and in decreasing the viscosity of the phenolic resin. The decrease in viscosity led to better wetting properties of NGP / phenolic

A general background, test plan, and some results of preliminary examinations of a carbon-carbon composite material are presented with emphasis on mechanical testing and inspection techniques. Experience with testing and evaluation was gained through tests of a low modulus carbon-carbon material, K-Karb C. The properties examined are the density - 1.55 g/cc; four point flexure strength in the warp - 137 MPa (19,800 psi) and the fill - 95.1 MPa (13,800 psi,) directions; and the warp interlaminar shear strength - 14.5 MPa (2100 psi). Radiographic evaluation revealed thickness variations and the thinner areas of the composite were scrapped. The ultrasonic C-scan showed attenuation variations, but these did not correspond to any of the physical and mechanical properties measured. Based on these initial tests and a survey of the literature, a plan has been devised to examine the effect of stress on the oxidation behavior, and the strength degradation of coated carbon-carbon composites. This plan will focus on static fatigue tests in the four point flexure mode in an elevated temperature, oxidizing environment.

Joining of carbon-carbon (C-C) composites by graphite formation, using manganese, magnesium, and aluminum interlayers, has been investigated. The process involved the formation of a metal carbide by chemical reaction between the metal interlayer and the composite, followed by the decomposition of the carbide and evaporation of the metal at elevated temperatures. The maximum bonding temperature in these experiments was 2,200 C. Bonding of composite specimens occurred when manganese or a powder mixture of aluminum and graphite was used as interlayers. Attempts to join C-C pieces using a magnesium interlayer were unsuccessful. The double notch shear strengths of the joints produced using Mn interlayers were very low and ranged from 0.15 to 1.61 MPa at test temperatures of 1,200 and 1,400 C. The interlayer, after completion of the joining operation, consisted, in most cases, only of graphite. The joints produced with aluminum plus graphite interlayers were even weaker, with strength values of 0.11 MPa or less. The presence of aluminum could be detected in some of these joints, suggesting incomplete dissociation of Al[sub 4]C[sub 3] at the maximum bonding temperature of 2,150 C.

Argonne National Laboratory is developing a glass bonded ceramic waste form for encapsulating the fission products and transuranics from the conditioning of metallic reactor fuel. This waste form is currently being scaled to the multi-kilogram size for encapsulation of actual high level waste. This paper will present characterization and durability testing of the ceramic waste form. An emphasis on results from application of glass durability tests such as the Product Consistency Test and characterization methods such as X-ray diffraction and scanning electron microscopy. The information presented is based on a suite of tests utilized for assessing product quality during scale-up and parametric testing.

Phosphorus-carbon bond formation from discrete transition metal complexes have been investigated through a combination of synthetic, spectroscopic, crystallographic, and computational methods. Reactive intermediates of the type (diphosphine)Pd(aryl)(P(O)(OEt)(2)) have been prepared, characterized, and studied as possible intermediates in metal-mediated coupling reactions. Several of the reactive intermediates were characterized crystallographicaliy, and a discussion of the solid state structures is presented. In contrast to other carbon-heteroelement bondforming reactions, palladium complexes containing electron-donating substituents on the aromatic fragment exhibited faster rates of reductive elimination. Large bite angle diphosphine ligands induced rapid rates of elimination, while bipyridine and small bite angle diphosphine ligands resulted in much slower rates of elimination. An investigation of the effect of typical impurities on the elimination reaction was carried out. While excess diphosphine, pyridine, and acetonitrile had little effect on the observed rate, the addition of water slowed the phosphorus-carbon bondforming reaction. Coordination of water to the complex was observed spectroscopically and crystallographically. Computational studies were utilized to probe the reaction pathways for P-C bond formation via Pd catalysis.

A process for providing vicinal dimethyl long chain between alkyl groups of organic compounds is described. The process uses intact or disrupted cells of various species of bacteria, particularly Thermoanaerobacter sp., Sarcina sp. and Butyrivibrio sp. The process can be conducted in an aqueous reaction mixture at room temperatures.

A process for providing vicinal dimethyl long chain between alkyl groups of organic compounds is described. The process uses intact or disrupted cells of various species of bacteria, particularly Thermoanaerobacter sp., Sarcina sp. and Butyrivibrio sp. The process can be conducted in an aqueous reaction mixture at room temperatures. 8 figs.

Glass-bonded zeolite is being considered as a candidate ceramic waste form for storing radioactive isotopes separated from spent nuclear fuel in the electrorefining process. To determine the stability of glass-bonded zeolite under irradiation, transmission electron microscope samples were irradiated using high energy helium, lead, and krypton. The major crystalline phase of the waste form, which retains alkaline and alkaline earth fission products, loses its long range order under both helium and krypton irradiation. The dose at which the long range crystalline structure is lost is about 0.4 dpa for helium and 0.1 dpa for krypton. Because the damage from lead is localized in such a small region of the sample, damage could not be recognized even at a peak damage of 50 dpa. Because the crystalline phase loses its long range structure due to irradiation, the effect on retention capacity needs to be further evaluated.

Using highly ductile acrylic adhesive, the present authors proposed a new technique of plastic bending of adhesively bonded sheet metals. In this process, the suppression of large transverse shear deformation occurring in the adhesive layer, which in some cases would induce the geometrical imperfection (so-called ‘gull-wing bend') and the delamination of the sheet, is one of the most important technical issues. In the present work, the effect of forming speed on bending deformation was investigated. From experimental observations in V-bending experiments of adhesively bonded aluminium sheets, as well as the corresponding numerical simulations which consider the viscoplasticity nature of the adhesive resin, it was found that the large shear deformation and ‘gull-wing bend' are successfully suppressed by high-speed forming since the deformation resistance of the adhesive resin becomes higher at a high strain rate.

A differential sputter yield measurement technique is described, which consists of a quartz crystal monitor that is swept at constant radial distance from a small target region where a high current density xenon ion beam is aimed. This apparatus has been used to characterize the sputtering behavior of various forms of carbon including polycrystalline graphite, pyrolytic graphite, and PVD-infiltrated and pyrolized carbon-carbon composites. Sputter yield data are presented for pyrolytic graphite and carbon-carbon composite over a range of xenon ion energies from 200 eV to 1 keV and angles of incidence from 0 deg (normal incidence) to 60 deg .

Two finite element analysis codes are used to model the effects of cooling on the dimensional stability of formed and bonded composite parts. The two analysis routines, one h-version and one p-version, are compared for modeling time, analysis execution time, and exactness of solution as compared to actual test results. A recommended procedure for predicting temperature effects on composite parts is presented, based on the results of this study.

PURPOSE The purpose of this study was to compare the fracture strength of the metal and the bond strength in metal-ceramic restorations produced by selective laser sintering (SLS) and by conventional casting (CAST). MATERIALS AND METHODS Non-precious alloy (StarLoy C, DeguDent, Hanau, Germany) was used in CAST group and metal powder (SP2, EOS GmbH, Munich, Germany) in SLS group. Metal specimens in the form of sheets (25.0 × 3.0 × 0.5 mm) were produced in accordance with ISO 9693:1999 standards (n=30). To measure the bond strength, ceramic was fired on a metal specimen and then three-point bending test was performed. In addition, the metal fracture strength was measured by continuing the application of the load. The values were statistically analyzed by performing independent t-tests (α=.05). RESULTS The mean bond strength of the SLS group (50.60 MPa) was higher than that of the CAST group (46.29 MPa), but there was no statistically significant difference. The metal fracture strength of the SLS group (1087.2 MPa) was lower than that of the CAST group (2399.1 MPa), and this difference was statistically significant. CONCLUSION In conclusion the balling phenomenon and the gap formation of the SLS process may increase the metal-ceramic bond strength. PMID:25177469

The electrometallurgical treatment of metallic spent nuclear fuel produces two high-level waste streams; cladding hulls and chloride salt. Argonne National Laboratory is developing a glass bonded sodalite waste form to immobilize the salt waste stream. The waste form consists of 75 Vol.% crystalline sodalite (containing the salt) with 25 Vol.% of an ''intergranular'' glassy phase. Microindentation fracture toughness measurements were performed on representative samples of this material using a Vickers indenter. Palmqvist cracking was confirmed by post-indentation polishing of a test sample. Young's modulus was measured by an acoustic technique. Fracture toughness, microhardness, and Young's modulus values are reported, along with results from scanning electron microscopy studies.

A method for making a lightweight cylinder block composed of carbon-carbon is disclosed. The use of carbon-carbon over conventional materials. such as cast iron or aluminum, reduces the weight of the cylinder block and improves thermal efficiency of the internal combustion reciprocating engine. Due to the negligible coefficient of thermal expansion and unique strength at elevated temperatures of carbon-carbon, the piston-to-cylinder wall clearance can be small, especially when the carbon-carbon cylinder block is used in conjunction with a carbon-carbon piston. Use of the carbon-carbon cylinder block has the effect of reducing the weight of other reciprocating engine components allowing the piston to run at higher speeds and improving specific engine performance.

A significant fraction of airframe structure consists of stiffened panels that are costly and difficult to fabricate. This program explored a potentially lower-cost processing route for producing such panels. The alternative process sought to apply concurrent superplastic forming and adhesive bonding of aluminum alloy sheets. Processing conditions were chosen to balance adequate superplasticity of the alloy with thermal stability of the adhesive. As a first objective, an air-quenchable, superplastic aluminum-lithium alloy and a low-volatile content, low-viscosity adhesive with compatible forming/curing cycles were identified. A four-sheet forming pack was assembled which consisted of a welded two-sheet core separated from the face sheets by a layer of adhesive. Despite some preliminary success, of over 30 forming trials none was completely successful. The main problem was inadequate superplasticity in the heat-affected zones of the rib welds, which generally fractured prior to completion of the forming cycle. The welds are a necessary component in producing internal ribs by the 'four-sheet' process. Other challenges, such as surface preparation and adhesive bonding, were adequately solved. But without the larger issue of tearing at the weld locations, complex panel fabrication by SPF/AB does not appear viable.

Superhydrophobic amorphous carbon/carbon nanotube nanocomposites are fabricated by plasma immersion ion implantation with carbon nanotube forests as a template. The microstructure of the fabricated nanocomposites shows arrays of carbon nanotubes capped with amorphous carbon nanoparticles. Contact angle measurements show that both advancing and receding angles close to 180° can be achieved on the nanocomposites. The fabrication here does not require patterning of carbon nanotubes or deposition of conformal coatings with low surface energy, which are usually involved in conventional approaches for superhydrophobic surfaces. The relationship between the observed superhydrophobicity and the unique microstructure of the nanocomposites is discussed.

The plane strain of adhesively bonded structures which consist of two different orthotropic adherents is considered. Assuming that the thicknesses of the adherends are constant and are small in relation to the lateral dimensions of the bonded region, the adherends are treated as plates. The transverse shear effects in the adherends and the in-plane normal strain in the adhesive are taken into account. The problem is reduced to a system of differential equations for the adhesive stresses which is solved in closed form. A single lap joint and a stiffened plate under various loading conditions are considered as examples. To verify the basic trend of the solutions obtained from the plate theory a sample problem is solved by using the finite element method and by treating the adherends and the adhesive as elastic continua. The plate theory not only predicts the correct trend for the adhesive stresses but also gives rather surprisingly accurate results.

Intermolecular hydrogen bonding in X3CH···NH3 (X = H, F, Cl, and Br) complexes has been studied by B3LYP, B3PW91, MP2, MP3, MP4, and CCSD methods using 6-311++G(d,p) and AUG-cc-PVTZ basis sets. These complexes could exist in both eclipsed (EC) and staggered (ST) forms. The differences between binding energies of EC and ST forms are negligible and all EC and ST shapes correspond to minimum stationary states. The order of stabilities of them is in an agreement with the results of atoms in molecules (AIM) and natural bond orbital (NBO) analyses. On the basis of low differences between binding energies, ST forms are more stable than EC forms in all complexes with the exception of Br3CH···NH3, which behaves just opposite. Although the differences between binding energies are negligible, they are consistent with the results of AIM analysis.

A glass-bonded ceramic waste form is being developed to immobilize radioactively contaminated chloride waste salts generated during the conditioning of spent sodium-bonded nuclear fuel for disposal. The waste salt is first mixed with zeolite A to occlude the salt into cavities in the zeolite structure. The salt-loaded zeolite is then mixed with a borosilicate glass and consolidated by hot isostatic pressing. During this process, the zeolite converts to the mineral sodalite, which retains most of the waste salt, and small amounts of halite are generated. Halite inclusions have been observed within micron- to submicron-sized pores that form within the glass phase in the vicinity of the sodalite/glass interface. These inclusions are important because they may contain small amounts of radionuclide contaminants (eg {sup 135}Cs and {sup 129}I),and may affect the corrosion behavior of the waste form. Optical microscopy, scanning electron microscopy, and transmission electron microscopy were used to characterize the chemical nature and distribution of halite inclusions in the waste form.

Catalysis by palladium derivatives is now one of the most important tools in organic synthesis. Whether researchers design palladium nanoparticles (NPs) or nanoparticles occur as palladium complexes decompose, these structures can serve as central precatalysts in common carbon-carbonbond formation. Palladium NPs are also valuable alternatives to molecular catalysts because they do not require costly and toxic ligands. In this Account, we review the role of "homeopathic" palladium catalysts in carbon-carbon coupling reactions. Seminal studies from the groups of Beletskaya, Reetz, and de Vries showed that palladium NPs can catalyze Heck and Suzuki-Miyaura reactions with aryl iodides and, in some cases, aryl bromides at part per million levels. As a result, researchers coined the term "homeopathic" palladium catalysis. Industry has developed large-scale applications of these transformations. In addition, chemists have used Crooks' concept of dendrimer encapsulation to set up efficient nanofilters for Suzuki-Miyaura and selective Heck catalysis, although these transformations required high PdNP loading. With arene-centered, ferrocenyl-terminated dendrimers containing triazolyl ligands in the tethers, we designed several generations of dendrimers to compare their catalytic efficiencies, varied the numbers of Pd atoms in the PdNPs, and examined encapsulation vs stabilization. The catalytic efficiencies achieved "homeopathic" (TON = 540 000) behavior no matter the PdNP size and stabilization type. The TON increased with decreasing the Pd/substrate ratio, which suggested a leaching mechanism. Recently, we showed that water-soluble arene-centered dendrimers with tri(ethylene glycol) (TEG) tethers stabilized PdNPs involving supramolecular dendritic assemblies because of the interpenetration of the TEG branches. Such PdNPs are stable and retain their "homeopathic" catalytic activities for Suzuki-Miyaura reactions for months. (TONs can reach 2.7 × 10(6) at 80 °C for aryl

A ceramic waste form (CWF) of glass bonded sodalite is being developed as a waste form for the long-term immobilization of fission products and transuranic elements from the U.S. Department of Energy's activities on spent nuclear fuel conditioning. A durable waste form was prepared by hot isostatic pressing (HIP) a mixture of salt-loaded zeolite powders and glass frit. During HIP the zeolite is converted to sodalite, and the resultant CWF is been completed for durations of up to 182 days. Four dissolution modes were identified: dissolution of free salt, dissolution of the aluminosilicate matrix of sodalite and the accompanying dissolution of occluded salt, dissolution of the boroaluminosilicate matrix of the glass, and ion exchange. Synergies inherent to the CWF were identified by comparing the results of the tests with pure glass and sodalite with those of the composite CWF.

In bacteria, disulfide bonds confer stability on many proteins exported to the cell envelope or beyond. These proteins include numerous bacterial virulence factors. Thus, bacterial enzymes that promote disulfide bond formation represent targets for compounds inhibiting bacterial virulence. Here, we describe a novel target- and cell-based screening methodology for identifying compounds that inhibit the disulfide bond-forming enzymes E. coli DsbB (EcDsbB) or M. tuberculosis VKOR (MtbVKOR). MtbVKOR can replace EcDsbB although the two are not homologues. Initial screening of 51,487 compounds yielded six specifically inhibiting EcDsbB. These compounds share a structural motif and do not inhibit MtbVKOR. A medicinal chemistry approach led us to select related compounds some of which are much more effective DsbB inhibitors than those found in the screen. These compounds inhibit purified DsbB and prevent anaerobic E. coli growth. Furthermore, these compounds inhibit all but one of the DsbBs of nine other gram-negative pathogenic bacteria tested. PMID:25686372

This paper deals with the temperature and rate-dependent elasto-viscoplasticity behaviour of a highly ductile acrylic adhesive and its effect on plastic bending of adhesively bonded sheet metals. Tensile lap shear tests of aluminium single-lap joints were performed at various temperature of 10-40°C at several tensile speeds. Based on the experimental results, a new constitutive model of temperature and rate-dependent elasto-viscoplasticity of the adhesive is presented. From V-bending experiments and the corresponding numerical simulation, it was found that the gull-wing bend is suppressed by high-speed forming at a lower temperature.

The paper concerns the elastic buckling behavior of a newly developed superplastically formed/diffusion-bonded (SPF/DB) orthogonally corrugated core sandwich plate. Uniaxial buckling loads were calculated for this type of sandwich plate with simply supported edges by using orthotropic sandwich plate theory. The buckling behavior of this sandwich plate was then compared with that of an SPF/DB unidirectionally corrugated core sandwich plate under conditions of equal structural density. It was found that the buckling load for the former was considerably higher than that of the latter.

The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon-nitrogen bondforming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions. PMID:26931222

Formulas and associated graphs for evaluating the effective elastic constants for a superplastically formed/diffusion bonded (SPF/DB) corrugated sandwich core, are presented. A comparison of structural stiffnesses of the sandwich core and a honeycomb core under conditions of equal sandwich core density was made. The stiffness in the thickness direction of the optimum SPF/DB corrugated core (that is, triangular truss core) is lower than that of the honeycomb core, and that the former has higher transverse shear stiffness than the latter.

Fifty-seven samples of model compounds, 4,4'-disubstituted benzylidene anilines, p-X-ArCH=NAr-p-Y were synthesized. Their infrared absorption spectra were recorded, and the stretching vibration frequencies νC=N of the C=N bridging bond were determined. New stretching vibration mode was proposed by means of the analysis of the factors affecting νC=N, that is there are mainly three modes in the stretching vibration of C=N bond: (I) polar double bondform C=N, (II) single bond-ion form C(+)-N(-) and (III) single bond-diradical form C-N. The contributions of the forms (I) and (II) to the change of νC=N can be quantified by using Hammett substituent constant (including substituent cross-interaction effects between X and Y groups), whereas the contribution of the form (III) can be quantified by employing the excited-state substituent constant. The most contribution of these three forms is the form (III), the next is the form (II), whose contribution difference was discussed with the viewpoint of energy requirements in vibration with the form (III) and form (II). PMID:27043872

Fifty-seven samples of model compounds, 4,4‧-disubstituted benzylidene anilines, p-X-ArCH = NAr-p-Y were synthesized. Their infrared absorption spectra were recorded, and the stretching vibration frequencies νCdbnd N of the Cdbnd N bridging bond were determined. New stretching vibration mode was proposed by means of the analysis of the factors affecting νCdbnd N, that is there are mainly three modes in the stretching vibration of Cdbnd N bond: (I) polar double bondform Cdbnd N, (II) single bond-ion form C+-N- and (III) single bond-diradical form Crad -Nrad . The contributions of the forms (I) and (II) to the change of νCdbnd N can be quantified by using Hammett substituent constant (including substituent cross-interaction effects between X and Y groups), whereas the contribution of the form (III) can be quantified by employing the excited-state substituent constant. The most contribution of these three forms is the form (III), the next is the form (II), whose contribution difference was discussed with the viewpoint of energy requirements in vibration with the form (III) and form (II).

A carbon composite structure, for example, an automotive engine piston, is made by preparing a matrix including of a mixture of non crystalline carbon particulate soluble in an organic solvent and a binder that has a liquid phase. The non crystalline particulate also contains residual carbon hydrogen bonding. An uncured structure is formed by combining the matrix mixture, for example, carbon fibers such as graphite dispersed in the mixture and/or graphite cloth imbedded in the mixture. The uncured structure is cured by pyrolyzing it in an inert atmosphere such as argon. Advantageously, the graphite reinforcement material is whiskered prior to combining it with the matrix mixture by a novel method involving passing a gaseous metal suboxide over the graphite surface.

An improved reciprocating internal combustion engine has a plurality of engine pistons, which are fabricated from carbon---carbon composite materials, in operative association with an engine cylinder block, or an engine cylinder tube, or an engine cylinder jug, all of which are also fabricated from carbon-carbon composite materials.

An improved reciprocating internal combustion engine has a plurality of engine pistons, which are fabricated from carbon-carbon composite materials, in operative association with an engine cylinder block, or an engine cylinder tube, or an engine cylinder jug, all of which are also fabricated from carbon-carbon composite materials.

Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically-bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. Magnesium phosphate ceramic has been developed to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests.

The main objective of this study is to develop an alternate, rapid and cost effective process for the fabrication of carbon/carbon (C/C) composite. Slurry moulding technique is adopted for the fabrication of C/C composite. Randomly oriented hybrid discrete carbon fiber (CF) reinforced and mesophase pitch (MP) derived matrix C/C composite is fabricated. Process parameters are optimized and repeatability is proved. The electrical conductivity of the composite fabricated through the developed process is found to be better than that fabricated through conventional processes. The other properties are also found to be competent. The randomly oriented C/C composite because of its mouldability is found suitable for various applications which require complex shapes.

Natural products containing N-N bonds exhibit important biological activity. Current methods for constructing N-N bonds have limited scope. An advanced understanding of the fundamental N-N bond formation/cleavage processes occurring at the transition-metal center would facilitate the development of catalytic reactions. Herein we present an N-N bond-forming reductive elimination, which proceeds via a mixed-valent Ni(II) -Ni(III) intermediate with a Ni-Ni bond order of zero. The discrete Ni(II) -Ni(III) oxidation states contrast with the cationic dimeric Ni analogue, in which both Ni centers are equivalent with an oxidation state of 2.5. The electronic structures of these mixed-valent complexes have implications for the fundamental understanding of metal-metal bonding interactions. PMID:27144682

... under said regulations. (b) Any packer, market agency, or dealer required to maintain a surety bond under these regulations may elect to maintain, in whole or partial substitution for such surety bond, a bond equivalent as provided below. The total amount of any such surety bond, equivalent, or...

... amount of coverage, Form MA-311. 308.531 Section 308.531 Shipping MARITIME ADMINISTRATION, DEPARTMENT OF... Insurance § 308.531 Endorsement of surety bond increasing or decreasing amount of coverage, Form MA-311. The..., Form MA-311, may be obtained from the American War Risk Agency or MARAD....

... amount of coverage, Form MA-311. 308.531 Section 308.531 Shipping MARITIME ADMINISTRATION, DEPARTMENT OF... Insurance § 308.531 Endorsement of surety bond increasing or decreasing amount of coverage, Form MA-311. The..., Form MA-311, may be obtained from the American War Risk Agency or MARAD....

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... amount of coverage, Form MA-311. 308.531 Section 308.531 Shipping MARITIME ADMINISTRATION, DEPARTMENT OF... Insurance § 308.531 Endorsement of surety bond increasing or decreasing amount of coverage, Form MA-311. The..., Form MA-311, may be obtained from the American War Risk Agency or MARAD....

A hollow core rotor blade for a turbine engine, comprising: a generally airfoil-shaped outer structure comprised of a superplastically formed, diffusion bonded sheet material, the outer structure having a trailing edge and a leading edge and being comprised of a matrix structure, with generally longitudinally oriented composite fibers being embedded within the superplastically formed material to increase the bending stiffness of the blade, the leading edge having an outer surface; and a hollow core spacing enclosed by the outer structure; wherein the outer surface of the leading edge is formed from a single sheet of material and is therefore structurally continuous and seamless, thereby allowing the rotor blade to be relatively lightweight, efficient, and durable, wherein each surface layer is comprised of an antifretting material having sufficient strength to withstand stresses between the blade and rotor during engine operation and sufficient ductility for forming into the manufactured shape; and wherein the shim is disposed between the dovetail and the dovetail slot, such that a portion of the first surface layer of the shims contacts at least a portion of each side face of the dovetail, and such that a portion of the second surface layer of the shim contacts at least a portion of each side wall of the dovetail slot.

Argonne National Laboratory has developed a glass-bonded sodalite waste form to immobilize the salt waste stream from electrometallurgical treatment of spent nuclear fuel. The waste form consists of 75 vol.% crystalline sodalite and 25 vol.% glass. Microindentation fracture toughness measurements were performed on this material and borosilicate glass from the Defense Waste Processing Facility using a Vickers indenter. Palmqvist cracking was confined for the glass-bonded sodalite waste form, while median-radial cracking occurred in the borosilicate glass. The elastic modulus was measured by an acoustic technique. Fracture toughness, microhardness, and elastic modulus values are reported for both waste forms.

Glass-bonded sodalite is being developed as a ceramic waste form (CWF) to immobilize radioactive fission products, actinides, and salt residues from electrometallurgical treatment of spent nuclear reactor fuel. The CWF consists of about 75 mass % sodalite, 25 mass % glass, and small amounts of other phases. This paper presents some results and interpretation of physical measurements to characterize the CWF structure, and dissolution tests to measure the release of matrix components and radionuclides from the waste form. Tests have been carried out with specimens of the CWF that contain rare earths at concentrations similar to those expected in the waste form. Parallel tests have been carried out on specimens that have uranium or plutonium as well as the rare earths at concentrations similar to those expected in the waste forms; in these specimens UCl{sub 3} forms UO{sub 2} and PuCl{sub 3} forms PuO{sub 2}. The normalized releases of rare earths in dissolution tests were found to be much lower than those of matrix elements (B, Si, Al, Na). When there is no uranium in the CWF, the release of cerium is two to ten times lower than the release of the other rare earths. The low release of cerium may be due to its tetravalent state in uranium-free CWF. However, when there is uranium in the CWF, the release of cerium is similar to that of the other rare earths. This trivalent behavior of cerium is attributed to charge transfer or covalent interactions among cerium, uranium, and oxygen in (U,Ce)O{sub 2}.

NASA sponsored the Aircraft Energy Efficiency (ACEE) program in 1976 to develop technologies to improve fuel efficiency. Laminar flow control was one such technology. Two approaches for achieving laminar flow were designed and manufactured under NASA sponsored programs: the perforated skin concept used at McDonnell Douglas and the slotted design used at Lockheed-Georgia. Both achieved laminar flow, with the slotted design to a lesser degree (JetStar flight test program). The latter design had several fabrication problems concerning springback and adhesive flow clogging the air flow passages. The Lockheed-Georgia Company accomplishments is documented in designing and fabricating a small section of a leading edge article addressing a simpler fabrication method to overcome the previous program's manufacturing problems, i.e., design and fabrication using advanced technologies such as diffusion bonding of aluminum, which has not been used on aerospace structures to date, and the superplastic forming of aluminum.

A reaction-bonded silicon carbide (RB-SiC) ceramic material (Carborundum's Cerastar RB-SIC) has been joined using a reaction forming approach. Microstructure and mechanical properties of three types of reaction-formed joints (350 micron, 50-55 micron, and 20-25 micron thick) have been evaluated. Thick (approximately 350 micron) joints consist mainly of silicon with a small amount of silicon carbide. The flexural strength of thick joints is about 44 plus or minus 2 MPa, and fracture always occurs at the joints. The microscopic examination of fracture surfaces of specimens with thick joints tested at room temperature revealed the failure mode to be typically brittle. Thin joints (<50-55 micron) consist of silicon carbide and silicon phases. The room and high temperature flexural strengths of thin (<50-55 micron) reaction-formed joints have been found to be at least equal to that of the bulk Cerastar RB-SIC materials because the flexure bars fracture away from the joint regions. In this case, the fracture origins appear to be inhomogeneities inside the parent material. This was always found to be the case for thin joints tested at temperatures up to 1350C in air. This observation suggests that the strength of Cerastar RB-SIC material containing a thin joint is not limited by the joint strength but by the strength of the bulk (parent) materials.

Many from within manufacturing industry consider superplastic forming (SPF) to be ‘high tech’, but it is often criticized as too complicated, expensive, slow and, in general, an unstable process when compared to other methods of manipulating sheet materials. Perhaps, the fundamental cause of this negative perception of SPF, and also of diffusion bonding (DB), is the fact that the current process of SPF/DB relies on indirect sources of heating to produce the conditions necessary for the material to be formed. Thus, heat is usually derived from the electrically heated platens of hydraulic presses, to a lesser extent from within furnaces and, sometimes, from heaters imbedded in ceramic moulds. Recent evaluations of these isothermal methods suggest they are slow, thermally inefficient and inappropriate for the process. In contrast, direct heating of only the material to be formed by modern, electrically efficient, lasers could transform SPF/DB into the first choice of designers in aerospace, automotive, marine, medical, architecture and leisure industries. Furthermore, ‘variable temperature’ direct heating which, in theory, is possible with a laser beam(s) may provide a means to control material thickness distribution, a goal of enormous importance as fuel efficient, lightweight structures for transportation systems are universally sought. This paper compares, and contrasts, the two systems and suggests how a change to laser heating might be achieved.

The quantitative analysis of molecular density matrices in terms of oriented quasi-atomic orbitals (QUAOs) is shown to yield detailed conceptual insight into the dissociation of dioxetane on the basis of ab initio wave functions. The QUAOs persist and can be followed throughout the reaction path. The kinetic bond orders and the orbital populations of the QUAOs quantitatively reveal the changes of the bonding interactions along the reaction path. At the transition state the OO bond is broken, and the molecule becomes a biradical. After the transition state the reaction path bifurcates. The minimum energy path gently descends from the transition state via a valley-ridge inflection point to a second saddle point, from which two new minimum energy paths lead to two equivalent formaldehyde dimers. The CC bond breaks, and the π-bonds of the formaldehyde fragments form in close vicinity of the second saddle point. The changes of the interactions in this region are elucidated by the analysis of the rearrangements of the QUAOs. PMID:26371996

In order to identify ruling mechanisms of tensile fracture of Carbon/Carbon composites (C/Cs), tensile tests were carried out for various C/Cs as functions of the density, heat treatment temperature, and interfacial strength between fiber and matrix. Three processing routes of preformed yarn, resin char, and HIP processes were adopted to densify C/Cs. These C/Cs were finally heat-treated at temperatures from 2273K to 3300K. The interfacial strength between fiber and matrix was varied by the selection of processing routes. As a result, two ruling failure mechanisms were identified. At density lower than 1.6g/cm3, the tensile fracture was controlled by stress transfer capability from the matrix to reinforcing fibers. However, at higher density than 1.6g/cm3, tensile strength was primarily governed by the interfacial strength between the matrix and fibers. Thus the latter mechanism is nearly same as ceramic matrix composites.

Summary The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bondforming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. PMID:25383109

Nitric oxide has been newly detected towards several star-forming clouds, including Orion-KL, Sgr B2(N), W33A, W51M, and DR21(OH) via its J = 3/2 --> 1/2 transitions near 150 GHz, using the FCRAO 14 m telescope. Both lambda-doubling components of NO were observed towards all sources. Column densities derived for nitric oxide in these clouds are N approximately 10(15)-10(16) cm-2, corresponding to fractional abundances of f approximately 0.5-1.0 x 10(-8), relative to H2. Towards Orion-KL, the NO line profile suggests that the species arises primarily from hot, dense gas. Nitric oxide may arise from warm material toward the other clouds as well. Nitric oxide in star-forming regions could be synthesized by high-temperature reactions, although the observed abundances do not disagree with values predicted from low-temperature, ion-molecule chemistry by more than one order of magnitude. The abundance of NO, unlike other simple interstellar nitrogen compounds, does appear to be reproduced by chemical models, at least to a good approximation. Regardless of the nature of formation of NO, it appears to be a common constituent of warm, dense molecular clouds. N-O bonds may therefore be more prevalent than previously thought. PMID:11538086

Water addition to carbon-carbon double bonds using hydratases is attracting great interest in biochemistry. Most of the known hydratases are involved in primary metabolism and to a lesser extent in secondary metabolism. New hydratases have recently been added to the toolbox, both from natural sources or artificial metalloenzymes. In order to comprehensively understand how the hydratases are able to catalyse the water addition to carbon-carbon double bonds, this review will highlight the mechanistic and stereochemical studies of the enzymatic water addition to carbon-carbon double bonds, focusing on the syn/anti-addition and stereochemistry of the reaction. PMID:25640045

The interlaminar tensile strength of 1000-tow T-300 fiber ACC-6 carbon-carbon composites was measured using the method of bonding the coupons to adherends at room temperature. The size, 0.70 to 1.963 inches maximum width or radius, and shape, round or square, of the test coupons were varied to determine if the test method was sensitive to these variables. Sixteen total variations were investigated and the results modeled.

In this study we demonstrate that molecular fragments, which can be readily coupled via a simple, in situ RO—C=OR bond-forming reaction, can subsequently undergo metal insertion–decarboxylation–recombination to generate Csp2–Csp3 bonds when subjected to metallaphotoredox catalysis. In this embodiment the conversion of a wide variety of mixed anhydrides (formed in situ from carboxylic acids and acyl chlorides) to fragment-coupled ketones is accomplished in good to high yield. A three-step synthesis of the medicinal agent edivoxetine is also described using this new decarboxylation–recombination protocol. PMID:26333771

We studied 1:1 and 1:2 complexes of triethylamine (TEA) with 5,5'-dibromo-2,2'-biphenol (DBBPh) in chloroform and acetonitrile solution using FT-IR and 1H NMR spectroscopy, and for comparison, the tetrabutylammonium 5,5'-dibromo-2,2'-biphenolate salt. In chloroform the 1:1 and 1:2 complexes are very stable and exist as hydrogen-bonded chains. In acetonitrile the 1:1 complexes are also stable, whereas the 1:2 complexes dissociate yielding protonated TEA and cyclic dimers of 5,5'-dibromo-2,2'-biphenol. The formation of cyclic dimers is favored in the case of the complex formed between tetrabutylammonium 5,5'-dibromo-2,2'-biphenolate and 5,5'-dibromo-2,2'-biphenol. All hydrogen bonds and hydrogen-bonded systems in the complexes studied show great proton polarizabity, since the protons may undergo fast fluctuations within these bonds.

Various anions were surrounded by n molecules of CF3H, which was used as a prototype CH donor solvent, and the structures and energies studied by M06-2X calculations with a 6-31+G∗∗ basis set. Anions considered included the halides F-, Cl-, Br- and I-, as well as those with multiple proton acceptor sites: CN-, NO3-, HCOO-, CH3COO-, HSO4-, H2PO4-, and anions with higher charges SO42-, HPO42- and PO43-. Well structured cages were formed and the average H-bond energy decreases steadily as the number of surrounding solvent molecules rises, even when n exceeds 6 and the CF3H molecules begin to interact with one another rather than with the central anion. Total binding energies are very nearly proportional to the magnitude of the negative charge on the anion. The free energy of complexation becomes more negative for larger n initially, but then reaches a minimum and begins to rise for larger values of n.

Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2]- was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

Metal catalyzed carbon-carbon (C–C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz){sub 2}, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz){sub 2}, the structure of [Li(Bz){sub 2}]{sup −} was drastically changed: Bz–Bz parallel form was rapidly fluctuated as a function of time, and a new C–C single bond was formed in the C{sub 1}–C{sub 1}′ position of Bz–Bz interaction system. In the hole capture, the intermolecular vibration between Bz–Bz rings was only enhanced. The mechanism of C–C bond formation in the electron capture was discussed on the basis of theoretical results.

Laboratory oxidation studies of reinforced carbon/carbon (RCC) are discussed with particular emphasis on the resulting microstructures. This study involves laboratory furnace (500-1500 C deg) and arc-jet exposures (1538 C deg) on various forms of RCC. RCC without oxidation protection oxidized at 800 and 1100 C deg exhibits pointed and reduced diameter fibers, due to preferential attack along the fiber edges. RCC with a SiC conversion coating exhibits limited attack of the carbon substrate at 500, 700 and 1500 C deg. However samples oxidized at 900, 1100, and 1300 C deg show small oxidation cavities at the SiC/carbon interface below through-thickness cracks in the SiC coating. These cavities have rough edges with denuded fibers and can be easily distinguished from cavities created in processing. Arc-jet tests at 1538 C deg show limited oxidation attack when the SiC coating and glass sealants are intact. When the SiC/sealant protection system is damaged, attack is extensive and proceeds through matrix cracks, creating denuded fibers on the edges of the cracks. Even at 1538 C deg, where diffusion control dominates, attack is non-uniform with fiber edges oxidizing in preference to the bulk fiber and matrix.

Carbon-carbon composites have become the material of choice for applications requiring strength and stiffness at very high temperatures (above 2000 C). These composites comprise carbon or graphite fibers embedded in a carbonized or graphitized matrix. In some applications, such as shielding sensitive electronics in very high temperature environments, the performance of these materials would be improved by lowering their electrical resistivity. One method to lower the resistivity of the composites is to lower the resistivity of the graphite fibers, and a proven method to accomplish that is intercalation. Intercalation is the insertion of guest atoms or molecules into a host lattice. In this study the host fibers were highly graphitic pitch-based graphite fibers, or vapor-grown carbon fibers (VGCF), and the intercalate was bromine. Intercalation compounds of graphite are generally thought of as being only metastable, but it has been shown that the residual bromine graphite fiber intercalation compound is remarkably stable, resisting decomposition even at temperatures at least as high as 1000 C. The focus of this work was to fabricate composite preforms, determine whether the fibers they were made from were still intercalated with bromine after processing, and determine the effect on composite resistivity. It was not expected that the resistivity would be lowered as dramatically as with graphite polymer composites because the matrix itself would be much more conductive, but it was hoped that the gains would be substantial enough to warrant its use in high-performance applications. In a collaborative effort supporting a Space Act Agreement between the NASA Glenn Research Center and Applied Sciences, Inc. (Cedarville, OH), laminar preforms were fabricated with pristine and bromine-intercalated pitch-based fibers (P100 and P100-Br) and VGCF (Pyro I and Pyro I-Br). The green preforms were carbonized at 1000 C and then heat treated to 3000 C. To determine whether the

Infections are a devastating complication of titanium alloy orthopedic implants. Current therapy includes antibiotic-impregnated bone cement, and antibiotic-containing coatings. We hypothesized that daptomycin, a Gram-positive peptide antibiotic, could prevent bacterial colonization on titanium alloy surfaces if covalently bonded via a flexible, hydrophilic spacer. We designed and synthesized a series of daptomycin conjugates for bonding to the surface of 1.0 cm2 Ti6Al4V foils through bisphosphonate groups, reaching a maximum yield of 180 pmol /cm2. Daptomycin-bonded foils killed 53±5% of a high challenge dose of 3×105 cfu Staphylococcus aureus ATCC 29213. PMID:20949909

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

This study was aimed to evaluate the biocompatibility and mechanical property of carbon/carbon composites. At first, carbon/carbon composites were prepared by chemical vapor deposition, and the mechanical property of carbon/carbon composites was tested. The biocompatibility of carbon/carbon composites was evaluated by cytotoxicity test, sensitization test, micronucleus test and implantation test. Mechanical property test showed such carbon/carbon composites are of good compression property and tension property. Cytotoxicity test showed that the leaching liquor of samples has no effect on the growth and proliferation of L-929 cells. The medullary micronucleus frequency of mouse was 2.3 per thousand +/- 0.7 per thousand in experiment group. The sensitization test showed that the skin of the subjects of experiment group had slight erythema and edema, which was 0.188 +/- 0.40 according to Magnusson and Kligman classification. Implantation test revealed that there was slight inflammation around the tissue after the implantation of sample. At 12 weeks, scanning electron microscopy and histopathological exam indicated that the samples of experiment group were of good histocompatibility; and in comparison with control group, there was no significant differences (P > 0.05). So these kinds of samples have good biocompatibility, mechanical property and prospects of clinical application. PMID:21374980

Reinforced carbon/carbon (RCC) is used to protect the wing leading edge and nose cap of the Space Shuttle Orbiter on re-entry. It is composed of a lay-up of carbon/carbon fabric protected by a SiC conversion coating. Due to the thermal expansion mismatch of the carbon/carbon and the SiC, the SiC cracks on cool-down from the processing temperature. The cracks act as pathways for oxidation of the carbon/carbon. A model for the diffusion controlled oxidation of carbon/carbon through machined slots and cracks is developed and compared to laboratory experiments. A symmetric cylindrical oxidation cavity develops under the slots, confirming diffusion control. Comparison of cross sectional dimensions as a function of oxidation time shows good agreement with the model. A second set of oxidation experiments was done with samples with only the natural craze cracks, using weight loss as an index of oxidation. The agreement of these rates with the model is quite reasonab

The ability to form multiple carbon-carbonbonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bondforming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bondforming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

A critical issue with oxidation protected carbon/carbon composites used for spacecraft thermal protection is the formation of coating pinholes. In laboratory experiments, artificial pinholes were drilled through SiC-coatings on a carbon/carbon material and the material was oxidized at 600, 1000, and 1400 C at reduced pressures of air. The attack of the carbon/carbon was quantified by both weight loss and a novel cross-sectioning technique. A two-zone, one dimensional diffusion control model was adapted to analyze this problem. Agreement of the model with experiment was reasonable at 1000 and 1400 C; however results at lower temperatures show clear deviations from the theory suggesting that surface reaction control plays a role.

An improved, lightweight, turbine housing unit for an intermittent combustion reciprocating internal combustion engine turbocharger is prepared from a lay-up or molding of carbon-carbon composite materials in a single-piece or two-piece process. When compared to conventional steel or cast iron, the use of carbon-carbon composite materials in a turbine housing unit reduces the overall weight of the engine and reduces the heat energy loss used in the turbocharging process. This reduction in heat energy loss and weight reduction provides for more efficient engine operation.

... section 7485, relating to bonds to stay assessment and collection of a deficiency pending review of a Tax.... 15 (see 31 CFR part 225). (2) Other surety acceptable in discretion of district director. Unless... in subchapter E of this chapter (Alcohol, Tobacco, and Other Excise Taxes)....

... section 7485, relating to bonds to stay assessment and collection of a deficiency pending review of a Tax.... 15 (see 31 CFR part 225). (2) Other surety acceptable in discretion of district director. Unless... in subchapter E of this chapter (Alcohol, Tobacco, and Other Excise Taxes)....

This elemental space radiator heat pipe is designed to operate in the 700 to 875 K temperature range. It consists of a C-C (carbon-carbon) shell made from poly-acrylonitride fibers that are woven in an angle interlock pattern and densified with pitch at high process temperature with integrally woven fins. The fins are 2.5 cm long and 1 mm thick, and provide an extended radiating surface at the colder condenser section of the heat pipe. The weave pattern features a continuous fiber bath from the inner tube surface to the outside edges of the fins to maximize the thermal conductance, and to thus minimize the temperature drop at the condenser end. The heat pipe and radiator element together are less than one-third the mass of conventional heat pipes of the same heat rejection surface area. To prevent the molten potassium working fluid from eroding the C C heat pipe wall, the shell is lined with a thin-walled, metallic tube liner (Nb-1 wt.% Zr), which is an integral part of a hermetic metal subassembly which is furnace-brazed to the inner surface of the C-C tube. The hermetic metal liner subassembly includes end caps and fill tubes fabricated from the same Nb-1Zr alloy. A combination of laser and electron beam methods is used to weld the end caps and fill tubes. A tungsten/inert gas weld seals the fill tubes after cleaning and charging the heat pipes with potassium. The external section of this liner, which was formed by a "Uniscan" rolling process, transitions to a larger wall thickness. This section, which protrudes beyond the C-C shell, constitutes the "evaporator" part of the heat pipe, while the section inside the shell constitutes the condenser of the heat pipe (see figure).

A coulometric titration is used for the determination of carbonatecarbon in geological materials. Carbon dioxide is evolved from the sample by the addition of 2 M perchloric acid, with heating, and is determined by automated coulometric titration. The coulometric titration showed improved speed and precision with comparable accuracy to gravimetric and gasometric techniques. ?? 1985.

Advanced repair and refurbishment technologies are critically needed for the thermal protection system of current space transportation system as well as for future Crew Exploration Vehicles (CEV). The damage to these components could be caused by impact during ground handling or due to falling of ice or other objects during launch. In addition, in-orbit damage includes micrometeoroid and orbital debris impact as well as different factors (weather, launch acoustics, shearing, etc.) during launch and re-entry. The GRC developed GRABER (Glenn Refractory Adhesive for Bonding and Exterior Repair) material has shown multiuse capability for repair of small cracks and damage in reinforced carbon-carbon (RCC) material. The concept consists of preparing an adhesive paste of desired ceramic with appropriate additives and then applying the paste to the damaged/cracked area of the RCC composites with adhesive delivery system. The adhesive paste cures at 100-120 C and transforms into a high temperature ceramic during simulated entry conditions. A number of plasma torch and ArcJet tests were carried out to evaluate the crack repair capability of GRABER materials for Reinforced Carbon-Carbon (RCC) composites. For the large area repair applications, integrated system for tile and leading edge repair (InSTALER) have been developed. In this presentation, critical in-space repair needs and technical challenges as well as various issues and complexities will be discussed along with the plasma performance and post test characterization of repaired RCC materials.

Advanced repair and refurbishment technologies are critically needed for the RCC-based thermal protection system of current space transportation system as well as for future Crew Exploration Vehicles (CEV). The damage to these components could be caused by impact during ground handling or due to falling of ice or other objects during launch. In addition, in-orbit damage includes micrometeoroid and orbital debris impact as well as different factors (weather, launch acoustics, shearing, etc.) during launch and re-entry. The GRC developed GRABER (Glenn Refractory Adhesive for Bonding and Exterior Repair) material has shown multiuse capability for repair of small cracks and damage in reinforced carbon-carbon (RCC) material. The concept consists of preparing an adhesive paste of desired ceramic with appropriate adhesives and then applying the paste to the damaged/cracked area of the RCC composites with adhesive delivery system. The adhesive paste cures at 100-120 C and transforms into a high temperature ceramic during simulated entry conditions. A number of plasma torch and ArcJet tests were carried out to evaluate the crack repair capability of GRABER materials for Reinforced Carbon-Carbon (RCC) composites. For the large area repair applications, PLASTER (Patch Laminates and Sealant Technology for Exterior Repair) based systems have been developed. In this presentation, critical in-space repair needs and technical challenges as well as various issues and complexities will be discussed along with the plasma performance and post test characterization of repaired RCC materials.

Recent research and development activities in joining and integration of carbon-carbon (C/C) composites to metals such as Ti and Cu-clad-Mo for thermal management applications are presented with focus on advanced brazing techniques. A wide variety of carbon-carbon composites with CVI and resin-derived matrices were joined to Ti and Cu-clad Mo using a number of active braze alloys. The brazed joints revealed good interfacial bonding, preferential precipitation of active elements (e.g., Ti) at the composite/braze interface. Extensive braze penetration of the inter-fiber channels in the CVI C/C composites was observed. The chemical and thermomechanical compatibility between C/C and metals at elevated temperatures is assessed. The role of residual stresses and thermal conduction in brazed C/C joints is discussed. Theoretical predictions of the effective thermal resistance suggest that composite-to-metal brazed joints may be promising for lightweight thermal management applications.

Collisions between I2+ and CO have been investigated using time-of-flight mass spectrometry at a range of centre-of-mass collision energies between 0.5 and 3.0 eV. Following I2++CO collisions, we detect I++CO+ from a single-electron transfer reaction and IO++C+ from bond-forming reactivity. Reaction-window calculations, based on Landau-Zener theory, have been used to rationalise the electron transfer reactivity and computational chemistry has been used to explore the [I-CO]2+ potential energy surface to account for the observation of IO+. In addition, collisions between I2+ and CS2 have been investigated over a range of centre-of-mass collision energies between 0.8 and 6.0 eV. Both single- and double-electron transfer reactions are observed in the I2+/CS2 collision system, an observation again rationalised by reaction-window theory. The monocations IS+ and IC+ are also detected following collisions of I2+ with CS2, and these ions are clearly products from a bond-forming reaction. We present a simple model based on the structure of the [I-CS2]2+ collision complex to rationalise the significantly larger yield of IS+ than IC+ in this bond-forming process.

Covalent organic frameworks (COFs) are excellent candidates for various applications. So far, successful methods for the constructions of COFs have been limited to a few condensation reactions based on only one type of covalent bond formation. Thus, the exploration of a new judicious synthetic strategy is a crucial and emergent task for the development of this promising class of porous materials. Here, we report a new orthogonal reaction strategy to construct COFs by reversible formations of two types of covalent bonds. The obtained COFs consisting of multiple components show high surface area and high H2 adsorption capacity. The strategy is a general protocol applicable to construct not only binary COFs but also more complicated systems in which employing regular synthetic methods did not work. PMID:25581488

H atom loss following near ultraviolet photoexcitation of gas phase 2-thiophenethiol molecules has been studied experimentally, by photofragment translational spectroscopy (PTS) methods, and computationally, by ab initio electronic structure calculations. The long wavelength (277.5 ≥ λphot ≥ 240 nm) PTS data are consistent with S-H bond fission after population of the first (1)πσ* state. The partner thiophenethiyl (R) radicals are formed predominantly in their first excited Ã(2)A' state, but assignment of a weak signal attributable to H + R(X[combining tilde](2)A'') products allows determination of the S-H bond strength, D0 = 27 800 ± 100 cm(-1) and the Ã-X[combining tilde] state splitting in the thiophenethiyl radical (ΔE = 3580 ± 100 cm(-1)). The deduced population inversion between the Ã and X[combining tilde] states of the radical reflects the non-planar ground state geometry (wherein the S-H bond is directed near orthogonal to the ring plane) which, post-photoexcitation, is unable to planarise sufficiently prior to bond fission. This dictates that the dissociating molecules follow the adiabatic fragmentation pathway to electronically excited radical products. π* ← π absorption dominates at shorter excitation wavelengths. Coupling to the same (1)πσ* potential energy surface (PES) remains the dominant dissociation route, but a minor yield of H atoms attributable to a rival fragmentation pathway is identified. These products are deduced to arise via unimolecular decay following internal conversion to the ground (S0) state PES via a conical intersection accessed by intra-ring C-S bond extension. The measured translational energy disposal shows a more striking change once λphot ≤ 220 nm. Once again, however, the dominant decay pathway is deduced to be S-H bond fission following coupling to the (1)πσ* PES but, in this case, many of the evolving molecules are deduced to have sufficiently near-planar geometries to allow passage through the

A carbon/carbon composite in which a carbon matrix containing a controlled amount of boron or a boron compound is reinforced with carbon fiber exhibits a low coefficient of friction, i.e., on the order of 0.04 to 0.1 at temperatures up to 600.degree. C., which is one of the lowest frictional coefficients for any type of carbonaceous material, including graphite, glassy carbon, diamond, diamond-like carbon and other forms of carbon material. The high degree of slipperiness of the carbon composite renders it particularly adapted for limiting friction and wear at elevated temperatures such as in seals, bearings, shafts, and flexible joints

In this paper irradiation behavior of carbon fibers and carbon-carbon composites are discussed in terms on simple microstructural models. Previous data are discussed in terms of these models. New data are presented for the irradiation-induced dimensional changes of selected carbon-carbon composites. The influence of fiber precursor on carbon- carbon irradiation performance is discussed.

The understanding of the fundamental physical properties of metal-organic and organic-organic interfaces is crucial for improving the performance of organic electronic devices. This is particularly true for (multilayer) systems containing several molecular species due to their relevance for donor-acceptor systems. A prototypical heteromolecular bilayer system is copper-II-phthalocyanine (CuPc) on 3,4,9,10-perylene-tetra-carboxylic-dianhydride (PTCDA) on Ag(111). In an earlier work we have reported a commensurate registry between both organic layers and an enhanced charge transfer from the Ag substrate into the organic bilayer film [Phys. Rev. Lett. 108, 106103 (2012), 10.1103/PhysRevLett.108.106103], which both indicate an unexpectedly strong intermolecular interaction across the organic-organic interface. Here we present new details regarding electronic and geometric structure for the same system. In particular, we provide evidence that the enhanced charge transfer from the substrate into the organic bilayer does not involve CuPc electronic states, hence, there is no significant charge transfer into the second organic layer. Furthermore, we report vertical bonding distances revealing a shortening of the PTCDA-Ag(111) distance upon CuPc adsorption. Thus, electronic and geometric properties (charge transfer and bonding distance, respectively) both indicate a strengthening of the PTCDA-Ag(111) bond upon CuPc adsorption. We explain these findings—in particular the correlation between CuPc adsorption and increased charge transfer into PTCDA—in a model involving an intermolecular screening mechanism.

Measurements of tunnelling and librational excitations for the methyl group in paracetamol and tunnelling excitations for the methyl group in acetanilide are reported. In both cases, results are compared with molecular mechanics calculations, based on the measured low temperature crystal structures, which follow an established recipe. Agreement between calculated and measured methyl group observables is not as good as expected and this is attributed to the presence of comprehensive hydrogen bond networks formed by the peptide groups. Good agreement is obtained with a periodic quantum chemistry calculation which uses density functional methods, these calculations confirming the validity of the one-dimensional rotational model used and the crystal structures. A correction to the Coulomb contribution to the rotational potential in the established recipe using semi-emipircal quantum chemistry methods, which accommodates the modified charge distribution due to the hydrogen bonds, is investigated.

Flammable materials have been studied in normal gravity and microgravity for many years. Photography plays a major role in the study of the combustion process giving a permanent visual record that can be analyzed. When these studies are extended to manned spacecraft, safety becomes a primary concern. The need for a high-pressure, flame-resistant, shatter-resistant window permitting photographic recording of combustion experiments in manned spacecraft prompted the development of a method for bonding Lexan and sapphire. Materials that resist shattering (e.g., Lexan) are not compatible with combustion experiments; the material loses strength at combustion temperatures. Sapphire is compatible with combustion temperatures in oxygen-enriched atmospheres but is subject to shattering. Combining the two materials results in a shatter-resistant, flame-resistant window. Combustion in microgravity produces a low-visibility flame; however, flame propagation and flame characteristics are readily visible as long as there is no deterioration of the image. Since an air gap between the Lexan and the sapphire would reduce transmission, a method was developed for bonding these unlike materials to minimize light loss.

GeSn-on-insulator (GeSnOI) on Silicon (Si) substrate was realized using direct wafer bonding technique. This process involves the growth of Ge1-xSnx layer on a first Si (001) substrate (donor wafer) followed by the deposition of SiO2 on Ge1-xSnx, the bonding of the donor wafer to a second Si (001) substrate (handle wafer), and removal of the Si donor wafer. The GeSnOI material quality is investigated using high-resolution transmission electron microscopy, high-resolution X-ray diffraction (HRXRD), atomic-force microscopy, Raman spectroscopy, and spectroscopic ellipsometry. The Ge1-xSnx layer on GeSnOI substrate has a surface roughness of 1.90 nm, which is higher than that of the original Ge1-xSnx epilayer before transfer (surface roughness is 0.528 nm). The compressive strain of the Ge1-xSnx film in the GeSnOI is as low as 0.10% as confirmed using HRXRD and Raman spectroscopy.

Three C-X bond formation mechanisms observed in the oxidation of (HBpz3)ReO(R)(OTf) [HBpz 3 = hydrotris(1-pyrazolyl)borate; R = Me, Et, and iPr; OTf = OSO2CF3] by dimethyl sulfoxide (DMSO) were investigated using quantum mechanics (M06//B3LYP DFT) combined with solvation (using the PBF Poisson-Boltzmann polarizable continuum solvent model). For R = Et we find the alkyl group is activated through α-hydrogen abstraction by external base OTf- with a free energy barrier of only 12.0 kcal/mol, leading to formation of acetaldehyde. Alternatively, ethyl migration across the M=O bond (leading to the formation of acetaldehyde and ethanol) poses a free energy barrier of 22.1 kcal/mol, and the previously proposed α-hydrogen transfer to oxo (a 2+2 forbidden reaction) poses a barrier of 44.9 kcal/mol. The rate-determining step to formation of the final product acetaldehyde is an oxygen atom transfer from DMSO to the ethylidene, with a free energy barrier of 15.3 kcal/mol. When R = iPr, the alkyl 1,2-migration pathway becomes the more favorable pathway (both kinetically and thermodynamically), with a free energy barrier (ΔG‡ = 11.8 kcal/mol) lower than α-hydrogen abstraction by OTf- (ΔG‡ = 13.5 kcal/mol). This suggests the feasibility of utilizing this type of migration to functionalize M-R to M-OR. We also considered the nucleophilic attack of water and ammonia on the Re-ethylidene α-carbon as a means of recovering two-electron-oxidized products from an alkane oxidation. Nucleophilic attack (with internal deprotonation of the nucleophile) is exothermic. However, the subsequent protonolysis of the Re-alkyl bond (to liberate an alcohol or amine) poses a barrier of 37.0 or 42.4 kcal/mol, respectively. Where comparisons are possible, calculated free energies agree very well with experimental measurements.

The Ti-metal/C-C composite joints were formed by reactive brazing with three commercial brazes, namely, Cu-ABA, TiCuNi, and TiCuSil. The joint microstructures were examined using optical microscopy, and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS). The results of the microstructure analysis indicate solute redistribution across the joint and possible metallurgical bond formation via interdiffusion, which led to good wetting and spreading.

The Ti-metal/C-C composite joints were formed by reactive brazing with three commercial brazes, namely, Cu-ABA, TiCuNi, and TiCuSil. The joint microstructures were examined using optical microscopy, and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS). The results of the microstructure analysis indicate solute redistribution across the joint which led to good wetting, spreading, and metallurgical bond formation via interdiffusion.

We report new self-assembled discotic liquid crystals exhibiting columnar mesophases at room temperature, which are constructed by intermolecular hydrogen bonding between the core of 1,3,5-trihydroxybenzene or 1,3,5-cyclohexanetricarboxylic acid and the peripheral molecules of isoquinoline derivatives. The mesomorphic properties of supramolecular liquid crystals were investigated by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction studies. The self-assembled liquid crystals exhibited rectangular columnar phases (Colro) with an ordered stacking structure of the mesogens in a column at room temperature, regardless of the type of the core molecule, due probably to the close-packed aromatic rings around a core molecule and the angular structure in three arms of the discotic mesogen. These room temperature columnar phases are rare examples for the discotic liquid crystals, and our findings in the present study provide a new way to prepare low melting columnar liquid crystalline materials for molecular electronics.

Dimeric aryl(hydro)boranes can provide suitable platforms for the synthesis of boron-containing graphene flakes through reductive B-B coupling. Two-electron reduction of 1,2:1,2-bis(4,4'-di-tert-butyl-2,2'-biphenylylene)diborane(6) (4) with LiNaph/THF establishes a B-B σ bond but can be accompanied by substituent redistribution. In the singly rearranged product, Li2[6], only one 1,2-phenyl shift has occurred. The doubly ring-contracted product, Li2[7], consists of two 9H-9-borafluorenyl moieties that are linked via their boron atoms. When the amount of LiNaph/THF is increased to 4 equiv, Li2[6] is subsequently observed as the dominant species. Addition of 11 equiv of LiNaph/THF results in over-reduction with hydride elimination to afford the doubly boron-doped dibenzo[g,p]chrysene Li2[1]. In contrast, excess KC8 reduces 4 to the corresponding dihydro-dibenzo[g,p]chrysene, K2[5], with a trans-HB-BH core. Hydride abstraction from K2[5] with 1 equiv of 4 leads to K[8], in which the central B-B bond is bridged by a single hydrogen atom. K[8] is also obtained upon treatment of 4 with 1 equiv of KC8. All products have been characterized by multinuclear NMR spectroscopy and X-ray crystallography. PMID:27111640

The objective of this Cooperative Research and Development Agreement (CRADA) between UT-Battelle, LLC (the "Contractor") and Synterials, Inc. (the "Participant") was to demonstrate promising processing methods, which can lead to producing Carbon-Carbon Composites (CCC), with tensile and interlaminar properties comparable to those of organic matrix composites and environmental stability at 1200 F for long periods of time. The participant synthesized carbon-carbon composites with two different fiber coatings and three different matrices. Both parties evaluated the tensile and interlaminar properties of these materials and characterized the microstructure of the matrices and interfaces. It was found that fiber coatings of carbon and boron carbide provided the best environmental protection and resulted in composites with high tensile strength.

Carbon-carbon composite are used in many applications including aircraft disk brakes, space shuttle leading edges, rocket inlet nozzles and exit cones, and are currently being considered for future aircraft structural components, because of their mechanical stability under adverse temperature conditions. Unfortunately, the processing of carbon-carbon composites, especially the first carbonizations, has a relatively low yield, because of in-process interply failure leading to catastrophic delaminations. Considerable amount of man-power, equipment time and material are lost. Here we report on the progress in the development of sensors for monitoring these catastrophic events during the first carbonization. Specifically, acoustic emission sensors and gas sensors are singled out as the most promising ones for monitoring the evolution of micro and macro-structural changes during the first carbonization. Analysis of the high temperature waveguide was undertaken to determine the optimum waveguide geometry so that only a single mode is allowed to propagate in the waveguide.

Objectives: The aim of this study was to evaluate the effect of two different cementation techniques of individually formed E-glass fiber-reinforced composite (FRC) post on bond strength and microleakage. Methods: The crowns of extracted third molars were removed and post preparation was carried out with parapost drills (diameter 1.5 mm). After application of bonding agents individually formed FRC posts (everStick POST, diameter 1.5 mm) were cemented into the post spaces with either ParaCem®Universal or self-adhesive RelyX™Unicem, using two different cementation techniques: 1) an “indirect (traditional) technique” where the post was prepolymerized prior application of luting cement and insertion into the post space or 2) a “direct technique” where the uncured post was inserted to the post space with luting cement and light-polymerized in situ at the same time. After water storage of 48 hours, the roots (n = 10/group) were cut into discs of thickness of 2 mm. A push-out force was applied until specimen fracture or loosening of the post. A microleakage test was carried out on roots which were not subjected to the loading test (n= 32) to evaluate the sealing capacity of the post-canal interface. The microleakage was measured using dye penetration depth under a stereomicroscope. Results: Higher bond strength values (p<0.05) and less microleakage (p<0.05) were obtained with the “direct technique” compared to the “indirect technique”. None of the FRC posts revealed any dye penetration between the post and the cement. Conclusions: The “direct technique” seems to be beneficial when cementing individually formed FRC posts. PMID:23986792

The U.S. Air Force Space Nuclear Thermal Propulsion (SNTP) program is placing high priority on maximizing specific impulse (ISP) and thrust-to-weight ratio in the development of a practical high-performance nuclear rocket. The turbopump design is driven by these goals. The liquid hydrogen propellant is pressurized and pumped to the reactor inlet by the turbopump assembly (TPA). Rocket propulsion is from rapid heating of the propellant from 180 R to thousands of degrees in the particle bed reactor (PBR). The exhausted propellant is then expanded through a high-temperature nozzle. A high-performance approach is to use an uncooled carbon-carbon nozzle and duct turbine inlet. Carbon-carbon components are used throughout the TPA hot section to obtain the high-temperature capability. Several carbon-carbon components are in development including structural parts, turbine nozzles/stators, and turbine rotors. The technology spinoff is applicable to conventional liquid propulsion engines and many other turbomachinery applications. 3 refs.

Carbon-carbon composites are a specialty class of materials having many unique properties making these composites attractive for a variety of demanding engineering applications. Chief among these properties are exceptional retention of mechanical properties at temperatures as high as 4000 F, excellent creep resistance, and low density (1.6 to 1.8 g/cu cm). Although carbon-carbon composites are currently in service in a variety of applications, much development work remains to be accomplished before these materials can be considered to be fully mature, realizing their full potential. Four recent technology advances holding particular promise for overcoming current barriers to the wide-spread commercialization of carbon-carbon composites are described. These advances are: markedly improved interlaminar strengths (more than doubled) of two dimensional composites achieved by whiskerization of the fabric reinforcing plies, simultaneously improved oxidation resistance and mechanical properties achieved by the incorporation of matrix-phase oxidation inhibitors based on carborane chemistry, improved oxidation resistance achieved by compositionally graded oxidation protective coatings, and markedly reduced processing times (hours as opposed to weeks or months) accomplished through a novel process of carbon infiltration and coatings deposition based on the use of liquid-phase precursor materials.

Carbon-Carbon Advanced Technologies, Inc. (C-CAT), has developed a high-melt coating for use in nozzle extensions in next-generation spacecraft. The coating is composed primarily of carbon-carbon, a carbon-fiber and carbon-matrix composite material that has gained a spaceworthy reputation due to its ability to withstand ultrahigh temperatures. C-CAT's high-melt coating embeds hafnium carbide (HfC) and zirconium diboride (ZrB2) within the outer layers of a carbon-carbon structure. The coating demonstrated enhanced high-temperature durability and suffered no erosion during a test in NASA's Arc Jet Complex. (Test parameters: stagnation heat flux=198 BTD/sq ft-sec; pressure=.265 atm; temperature=3,100 F; four cycles totaling 28 minutes) In Phase I of the project, C-CAT successfully demonstrated large-scale manufacturability with a 40-inch cylinder representing the end of a nozzle extension and a 16-inch flanged cylinder representing the attach flange of a nozzle extension. These demonstrators were manufactured without spalling or delaminations. In Phase II, C-CAT worked with engine designers to develop a nozzle extension stub skirt interfaced with an Aerojet Rocketdyne RL10 engine. All objectives for Phase II were successfully met. Additional nonengine applications for the coating include thermal protection systems (TPS) for next-generation spacecraft and hypersonic aircraft.

A method for forming at least one product silane, comprising reacting a transition metal hydride with a starting silane in a presence of a catalyst and at a temperature that exceeds a threshold temperature associated with said reacting.

Local energy levels produced by dislocations at the interface between bonded n- and p-Si wafers are studied by deep level transient spectroscopy and by a new technique for the detection of impurity luminescence, induced by the occupation of electron states upon the application of electric pulses (the pulsed trap-refilling-enhanced luminescence technique). It is established that only the shallow levels of the dislocation network, with activation energies of about 0.1 eV, are responsible for the D1 dislocation-related luminescence band in both n- and p-type samples. The occupation of deep levels has no effect on the D1-band intensity. A model of coupled neutral trapping centers for charge carriers is proposed. In this model, the difference between the energy position of the D1 band (0.8 eV) and the corresponding interlevel energy spacing (0.97 eV) is attributed to the Coulomb interaction between charge carriers trapped at the levels.

Carbon–sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5‧-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate.

Carbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5'-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate. PMID:27102684

Argonne National Laboratory has developed a ceramic waste form to immobilize the salt waste from electrometallurgical treatment of spent nuclear fuel. The process is being scaled up to produce bodies of 100 Kg or greater. With conventional heating, heat transfer through the starting powder mixture necessitates long process times. Coupling of 2.45 GHz radiation to the starting powders has been demonstrated. The radiation couples most strongly to the salt occluded zeolite powder. The results of these experiments suggest that this ceramic waste form could be produced using microwave heating alone, or by using microwave heating to augment conventional heating.

The Carbon-Carbon Space Radiator Partnership (CSRP), an informal partnership of Government and industrial personnel, was formed to promote the use of Carbon-carbon composites (C-C) as engineering materials for spacecraft thermal management applications . As a part of this effort the partnership has built a structural radiator for the Earth Orbiter - 1 (EO-1) spacecraft. This radiator, using C-C face-sheets with an aluminum honeycomb core, will demonstrate both the thermal and structural properties of C-C under actual service conditions as well as provide performance data from space flight. This paper will present results from the design of the radiator, the thermal/mechanical tests of the facesheet materials, and sub-component test results on the C-C/Al honeycomb sandwich material. The 29- by 28-inch radiator was designed to support two electronics boxes with a combined heat output of 60 watts maximum and a weight of 58 lbs. The analysis of the radiator design shows that the radiator constructed with 20-mil-thick facesheets of a P30-fiber-reinforced C-C from BFGoodrich is able to meet or exceed all the required thermal and mechanical requirements.

Composite laminates that consist of two or more layers find widespread applications in a variety of engineering structures. In the computational modelling of composite laminates, the layers can be stacked together and connected conveniently at the nodes by using multiple-point constraints (MPCs). However, this type of modelling leads to weakening of the kinematic constraint conditions imposed by the bond between the juxtaposed layers and as a consequence, MPCs application at the nodes produces behaviour that is softer than the perfectly bonded composite beam behaviour. The work herein shows that when kinematic conditions for composite action are weakly imposed in the variational form, they can be enforced in the point-wise sense by proper selection of the interpolation field or otherwise reinforced by using variational multiscale approach without modifying the kinematic model. The originality of the approach presented herein is in the interpretation of the MPCs application as the solution in a superfluously extended space because of the weakening in the kinematic constraints. It is shown that the perfect bond between the composite beam layers can be recovered by excluding the identified fine-scale effect from the solution of the multiple point constraint application. The convergence characteristic of the finite element formulation is also improved by using the variational multi-scale approach. It is also shown that the fine-scale effects can be represented by using extra fictitious elements and springs, which offers a direct correction technique in modelling of composite beams that is especially useful when access to the numerical procedure is limited.

Nitric oxide has been newly detected toward several star-forming clouds, including Orion-KL, Sgr B2(N), W33A, W51M, and DR21(OH) via its J = 3/2-1/2 transitions near 150 GHz, using the FCRAO 14 m telescope. Both lambda-doubling components of NO were observed toward all sources. Column densities derived for nitric oxide in these clouds are 10 to the 15th-10 to the 16th/sq cm, corresponding to fractional abundances of 0.5-1.0 x 10 to the -8th, relative to H2. Toward Orion-KL, the NO line profile suggests that the species arises primarily from hot, dense gas. Nitric oxide may arise from warm material toward the other clouds as well. Nitric oxide in star-forming regions could be synthesized by high-temperature reactions, although the observed abundances do not disagree with values predicted from low-temperature, ion-molecule chemistry by more than one order of magnitude.

Carbon-carbon composite materials offer greater thermal efficiency, stiffness to weight ratio, tailorability, and dimensional stability than aluminum. These lightweight thermal materials could significantly reduce the overall cost associated with satellite thermal control and weight. However, the high cost and long lead-time for carbon-carbon manufacture have limited their widespread usage. Consequently, an informal partnership between government and industrial personnel called the Carbon-Carbon spacecraft Radiator Partnership (CSRP) was created to foster carbon- carbon composite use for thermally and structurally demanding space radiator applications. The first CSRP flight opportunity is on the New Millennium Program Earth Orbiter-1 (EO-1) spacecraft, scheduled for launch in late 1999. For EO-1, the CSRP designed and fabricated a Carbon-Carbon Radiator with carbon-carbon facesheets and aluminum honeycomb core, which will also serve as a structural shear panel.

A hydroburst test of the aft portion of the PAM-D exit cone and the test procedure are described in detail. The hydrostatic pressure required to buckle the cone was 9.75 psi. Meanwhile, the PAM-D exit cone was modeled using the finite element method and a theoretical bucking pressure (8.76 psi) was predicted using the SPAR finite element code. The modeling technique employed is discussed. By comparing the theoretical to predicted critical pressures, this report verifies the modeling technique and calculates a material knockdown factor for the carbon-carbon exit cone.

The failure mechanisms of 2D carbon/carbon (C/C) woven laminates have been determined under inplane biaxial compression loads, and the associated failure envelopes that account for the effect of matrix-type and loading directions were also obtained. The failure was in the form of micro-kinking of fiber bundles, interspersed with localized interply delaminations to form an overall shear fault. The shear fault was aligned with the major axis of loading except at above 75% of balanced biaxial compressive stress where failure occurred along both axes. Although the biaxial strength varied significantly with the ratio of in-plane principal stresses, R, there was no variation in the local failure mechanisms. Accordingly, it was found that the samples fail upon achieving a critical strain along the primary axis of loading.

Carbon-carbon composites have many beneficial properties for use in aerospace applications, including their high specific strength and modulus at elevated temperatures. However, they share with all carbon based substances a strong tendency to burn when heated in air. In order to exploit their good qualities, it is necessary to slow or prevent their oxidation during use. Molecular inhibiters offer protection with the advantage of being able to form a homogeneous solution with the resin. Since boron oxides are known to provide the desired kind of protection, molecular compounds based on boron seem reasonable candidates to test as inhibitors. Performance tests indicated that carboranes are excellent materials for obtaining high uniform loadings of boron inhibitors in glassy carbon materials and thus reducing their rates of oxidation. Further, there is evidence that the use of substituted derivatives could provide more complete and thorough forms of protection.

The peptide bond-forming reagents 1-hydroxy-7-azabenzotriazole (HOAt, CAS 39968-33-7) and O-(7-Azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU, CAS 148893-10-1) either have structural alerts, unclassified features or are considered out of domain when evaluated for potential mutagenicity with in silico programs DEREK and CaseUltra. Since they are commonly used reagents in pharmaceutical drug syntheses, they may become drug substance or drug product impurities and would need to be either controlled to appropriately safe levels or tested for mutagenicity. Both reagents were tested in the bacterial reverse mutation (Ames) test at Covance, under GLP conditions, following the OECD test guideline and ICH S2(R1) recommendations and found to be negative. Our data show that HOAt and HATU-common pharmaceutical synthesis reagents-are not mutagenic, and can be treated as ordinary drug impurities. PMID:26840011

The application of the superplastic forming/diffusion bonding (SPF/DB) process to supersonic cruise research is investigated. The capability of an SPF/DB titanium structure to meet the structural requirements of the inner wing area of the NASA arrow-wing advanced supersonic transport design is evaluated. Selection of structural concepts and their optimization for minimum weight, SPF/DB process optimization, fabrication of representative specimens, and specimen testing and evaluation are described. The structural area used includes both upper and lower wing panels, where the upper wing panel is used for static compression strength evaluation and the lower panel, in tension, is used for fracture mechanics evaluations. The individual test specimens, cut from six large panels, consist of 39 static specimens, 10 fracture mechanics specimens, and one each full size panel for compression stability and fracture mechanics testing. Tests are performed at temperatures of -54 C (-65 F), room temperature, and 260 C (500 F).

Investigations of failures of components made of reinforced carbon/carbon show eddy-current flaw-detection techniques applicable to these components. Investigation focused on space shuttle parts, but applicable to other parts made of carbon/carbon materials. Techniques reveal cracks, too small to be detected visually, in carbon/carbon matrix substrates and in silicon carbide coates on substrates. Also reveals delaminations in carbon/carbon matrices. Used to characterize extents and locations of discontinuities in substrates in situations in which ultrasonic techniques and destructive techniques not practical.

We introduce a new technique using resonant soft x-ray scattering for characterizing heterogeneous chemical structure at nanometer length scales in polymers, biological material, and other soft matter. Resonant enhancements bring new contrast mechanisms and increased sensitivity to bridge a gap between bond-specific contrast in chemical sensitive imaging and the higher spatial resolution of traditional small-angle scattering techniques. We illustrate sensitivity to chemical bonding with the resonant scattering near the carbon K edge from latex spheres of differing chemistry and sizes. By tuning to x-ray absorption resonances associated with particular carbon-carbon or carbon-oxygen bonds we can isolate the scattering from different phases in a 2-phase mixture. We then illustrate this increased scattering contrast with a study of the templating process to form nanometer scale pores in 100 nm thick polymer films.

The objective of this study is to improve the understanding of the stress distributions and failure mechanisms experienced by carbon-carbon composite aircraft brake discs using finite element (FE) analyses. The project has been carried out in association with Dunlop Aerospace as an EPSRC CASE studentship. It therefore focuses on the carbon-carbon composite brake disc material produced by Dunlop Aerospace, although it is envisaged that the approach will have broader applications for modelling and mechanical testing of carbon-carbon composites in general. The disc brake material is a laminated carbon-carbon composite comprised of poly(acrylonitrile) (PAN) derived carbon fibres in a chemical vapour infiltration (CVI) deposited matrix, in which the reinforcement is present in both continuous fibre and chopped fibre forms. To pave the way for the finite element analysis, a comprehensive study of the mechanical properties of the carbon-carbon composite material was carried out. This focused largely, but not entirely, on model composite materials formulated using structural elements of the disc brake material. The strengths and moduli of these materials were measured in tension, compression and shear in several orientations. It was found that the stress-strain behaviour of the materials were linear in directions where there was some continuous fibre reinforcement, but non-linear when this was not the case. In all orientations, some degree of non-linearity was observed in the shear stress-strain response of the materials. However, this non-linearity was generally not large enough to pose a problem for the estimation of elastic moduli. Evidence was found for negative Poisson's ratio behaviour in some orientations of the material in tension. Additionally, the through-thickness properties of the composite, including interlaminar shear strength, were shown to be positively related to bulk density. The in-plane properties were mostly unrelated to bulk density over the range of

Oxidation protection for the Orbiter reinforced carbon-carbon (RCC consists of three components: silicon carbide coating, tetraethyl orthosilicate (TEOS) impregnated into the carbon substrate and a silicon based surface sealant (designated Type A). The Orbiter Type A sealant is being consumed each mission, which results in increased carbon-carbon substrate mass loss, which adversely impacts the mission life of the RCC components. In addition, the sealant loss in combination with launch pad contamination (salt deposit and zinc oxide) results in RCC pinholes. A sealant refurbishment schedule to maintain mission life and minimize affects of pin hole formation has been implemented in the Orbiter maintenance schedule. The objective of this investigation is to develop an advanced sealant system for the RCC that extends the refurbishment schedule by reducing sealant loss/pin hole formation and that can be applied to existing Orbiter RCC components. This paper presents the results of arc jet screening tests conducted on several sealants that are being considered for application to the Orbiter RCC.

In this study, coated reinforced carbon-carbon (RCC) samples of similar structure and composition as that from the NASA space shuttle orbiter s thermal protection system were fabricated with slots in their coating simulating craze cracks. These specimens were used to study oxidation damage detection and characterization using NDE methods. These specimens were heat treated in air at 1143 and 1200 C to create cavities in the carbon substrate underneath the coating as oxygen reacted with the carbon and resulted in its consumption. The cavities varied in diameter from approximately 1 to 3 mm. Single-sided NDE methods were used since they might be practical for on-wing inspection, while x-ray micro-computed tomography (CT) was used to measure cavity sizes in order to validate oxidation models under development for carbon-carbon materials. An RCC sample having a naturally-cracked coating and subsequent oxidation damage was also studied with x-ray micro-CT. This effort is a follow-on study to one that characterized NDE methods for assessing oxidation damage in an RCC sample with drilled holes in the coating. The results of that study are briefly reviewed in this article as well. Additionally, a short discussion on the future role of simulation to aid in these studies is provided.

[{Ni(dmpe)}(2)(μ-SiHPh(2))(2)] (dmpe = 1,2-bis(dimethylphosphino)ethane) reacted with PhC≡CPh to yield fluorescent 1,2-bis{(E)-1,2-diphenylethenyl}-1,1,2,2-tetraphenyldisilane via addition of the Si-H bond of the ligand to the alkyne and subsequent coupling of the tertiary silyl ligands forming the Si-Si bond. PMID:22241522

Results are presented for a study to determine the mechanisms involved in a high-temperature pack cementation process which provides a silicon carbide coating on a carbon-carbon composite. The process and materials used are physically and chemically analyzed. Possible reactions are evaluated using the results of these analytical data. The coating is believed to develop in two stages. The first is a liquid controlled phase process in which silicon carbide is formed due to reactions between molten silicon metal and the carbon. The second stage is a vapor transport controlled reaction in which silicon vapors react with the carbon. There is very little volume change associated with the coating process. The original thickness changes by less than 0.7%. This indicates that the coating process is one of reactive penetration. The coating thickness can be increased or decreased by varying the furnace cycle process time and/or temperature to provide a wide range of coating thicknesses.

This paper presents results from arc jet tests conducted at the NASA Johnson Space Center on reinforced carbon-carbon (RCC) samples subjected to hypervelocity impact. The RCC test specimens are representative of RCC components used on the Space Shuttle Orbiter. The arc jet testing established the oxidation characteristics of RCC when hypervelocity projectiles, simulating meteoroid/orbital debris, impact the RCC material. In addition to developing correlations for use in trajectory simulations, we discuss analytical modeling of the increased material oxidation in the impacted area using measured hole growth data. Entry flight simulations are useful in assessing the increased Space Shuttle RCC component degradation as a result of impact damage and the hot gas flow through an enlarging hole into the wing leading-edge cavity.

Carbon/carbon (C/C) composite material was investigated by means of small-angle as well as wide-angle elastic neutron scattering. The C/C-composites were built up from bi-directionally woven fabrics from PAN-based carbon fibers. Pre-impregnation with phenolic resin was followed by pressure curing and carbonization at 1000 °C and a final heat treatment at either 1800 or 2400 °C. Measurements of the samples were performed in orientations arranging the carbon fibers, respectively, parallel and perpendicular to the incoming beam. Structural features of the fibers as well as the inherently existing pores are presented and the influence of the heat treatment is discussed. The results are compared to earlier X-ray investigations of carbon fibers and C/C-composites.

This report discusses development and proof-of-concept testing of a new lightweight carbon-carbon (C-C) space radiator heat pipe developed under the NASA Civil Space Technology Initiative (CSTI) High Capacity Power Program. The heat pipe was filled with potassium working fluid and tested for 11 hours including startup from ambient temperature with the working fluid initially in the frozen state to near 700 K condenser temperature. Steady-state heat pipe input power during testing was facility limited to about 300 watts, representing about 50 percent of the design input power. Post test inspection showed the heat pipe to be in excellent condition after eight thermal cycles from ambient to steady-state operating temperature. Potential applications, ranging from small spacecraft heat rejection to aircraft and terrestrial uses, are discussed.

The extensive investigation following the Space Shuttle Orbiter Columbia accident of February 1, 2003 determined that hot gases entered the wing through a breach in the protective reinforced carbon/carbon (RCC) leading edge. In the current study, the exposed edges of the recovered RCC from the vicinity of the breach are examined with scanning electron microscopy and Raman spectroscopy. Electron microscopy of the exposed edges revealed regions of pointed carbon fibers, characteristic of exposure to high temperature oxidizing gases. The Raman technique relates the observed 1350 and 1580 to 1600 cm(-1) bands to graphitic dom ains and their corresponding temperatures of formation. Some of the regions showed evidence of exposure temperatures beyond 2700 ?C during the accident.

Since pyrolyzed carbon has a higher electrical conductivity than most polymers, carbon-carbon composites would be expected to have higher electromagnetic interference (EMI) shielding ability than polymeric resin composites. A rule of mixtures model of composite conductivity was used to calculate the effect on EMI shielding of substituting a pyrolyzed carbon matrix for a polymeric matrix. It was found that the improvements were small, no more than about 2 percent for the lowest conductivity fibers (ex-rayon) and less than 0.2 percent for the highest conductivity fibers (vapor grown carbon fibers). The structure of the rule of mixtures is such that the matrix conductivity would only be important in those cases where it is much higher than the fiber conductivity, as in metal matrix composites.

Carboxyl (COO-) vibrational modes of two amino acids histidine and glycine in D2O solution were investigated by temperature-dependent FTIR spectroscopy and temperature-jump nanosecond time-resolved IR difference absorbance spectroscopy. The results show that hydrogen bonds are formed between amino acid molecules as well as between the amino acid molecule and the solvent molecules. The asymmetric vibrational frequency of COO- around 1600-1610 cm-1 is blue shifted when raising temperature, indicating that the strength of the hydrogen bonds becomes weaker at higher temperature. Two bleaching peaks at 1604 and 1612 cm-1 were observed for histidine in response to a temperature jump from 10 °C to 20 °C. The lower vibrational frequency at 1604 cm-1 is assigned to the chain COO- group which forms the intermolecular hydrogen bond with NH3+ group, while the higher frequency at 1612 cm-1 is assigned to the end COO- group forming hydrogen bonds with the solvent molecules. This is because that the hydrogen bonds in the former are expected to be stronger than the latter. In addition the intensities of these two bleaching peaks are almost the same. In contrast, only the lower frequency at 1604 cm-1 bleaching peak has been observed for glycine. The fact indicates that histidine molecules form a dimer-like intermolecular chain while glycine forms a relatively longer chain in the solution. The rising phase of the IR absorption kinetics in response to the temperature-jump detected at 1604 cm-1 for histidine is about 30+/-10 ns, within the resolution limit of our instrument, indicating that breaking or weakening the hydrogen bond is a very fast process.

Two crystal structures of the major pilin SpaD from C. diphtheriae have been determined at 1.87 and 2.5 Å resolution. The N-terminal domain is found to contain an isopeptide bond that forms slowly over time in the recombinant protein. Given its structural context, this provides insight into the relationship between internal isopeptide-bond formation and pilus assembly. The Gram-positive organism Corynebacterium diphtheriae, the cause of diphtheria in humans, expresses pili on its surface which it uses for adhesion and colonization of its host. These pili are covalent protein polymers composed of three types of pilin subunit that are assembled by specific sortase enzymes. A structural analysis of the major pilin SpaD, which forms the polymeric backbone of one of the three types of pilus expressed by C. diphtheriae, is reported. Mass-spectral and crystallographic analysis shows that SpaD contains three internal Lys–Asn isopeptide bonds. One of these, shown by mass spectrometry to be located in the N-terminal D1 domain of the protein, only forms slowly, implying an energy barrier to bond formation. Two crystal structures, of the full-length three-domain protein at 2.5 Å resolution and of a two-domain (D2-D3) construct at 1.87 Å resolution, show that each of the three Ig-like domains contains a single Lys–Asn isopeptide-bond cross-link, assumed to give mechanical stability as in other such pili. Additional stabilizing features include a disulfide bond in the D3 domain and a calcium-binding loop in D2. The N-terminal D1 domain is more flexible than the others and, by analogy with other major pilins of this type, the slow formation of its isopeptide bond can be attributed to its location adjacent to the lysine used in sortase-mediated polymerization during pilus assembly.

Exfoliated graphite-based carbon/carbon composites were prepared using sequence processes of phenolic resin alcohol solution impregnation, carbonization and carbon dioxide (or steam) activation. The textural/structural characteristics of the composites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption and mercury porosimetry. The results indicated that the composites were composed of graphite and amorphous carbon. On the surface, the worm-like particles were covered by pyrolytic carbon, which also penetrated into parts of the interior pores of the particles. Macropores still remained in the composite, whereas micropores which were formed by the activation of pyrolytic carbon contributed to most of the pore volume.

... 25 Indians 1 2014-04-01 2014-04-01 false What is the release process for a performance bond or alternative form of security under a WSR lease? 162.561 Section 162.561 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR LAND AND WATER LEASES AND PERMITS Wind and Solar Resource Leases Wsr Lease...

... 25 Indians 1 2013-04-01 2013-04-01 false What is the release process for a performance bond or alternative form of security under a WSR lease? 162.561 Section 162.561 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR LAND AND WATER LEASES AND PERMITS Wind and Solar Resource Leases Wsr Lease...

In wafer-level packaging of microelectromechanical (MEMS) devices a lid wafer is bonded to a MEMS wafer in a predermined aligned relationship. Portions of the lid wafer are removed to separate the lid wafer into lid portions that respectively correspond in alignment with MEMS devices on the MEMS wafer, and to expose areas of the MEMS wafer that respectively contain sets of bond pads respectively coupled to the MEMS devices.

The feasibility of using carbon-carbon recuperators in closed-Brayton-cycle (CBC) nuclear space power conversion systems (PCS) was assessed. Recuperator performance expectations were forecast based on projected thermodynamic cycle state values for a planetary mission. Resulting thermal performance, mass and volume for a plate-fin carbon-carbon recuperator were estimated and quantitatively compared with values for a conventional offset-strip-fin metallic design. Material compatibility issues regarding carbon-carbon surfaces exposed to the working fluid in the CBC PCS were also discussed.

An attractive intermolecular interaction which has been called "halogen bonding" exists between the nitrogen, sulfur, or oxygen atoms present in HC motifs and the iodine atom of PFC residues. The "halogen bonding" is strong enough to overcome the low affinity existing between PFC and HC compounds, driving their self-assembly into supramolecular architectures. The non-covalent co-polymer formed by 1,2-diiodotetrafluoroethane with diazabicyclooctane has been prepared and characterised by FT-IR and -Raman spectroscopies. We propose the changes shown by the vibrational spectra of single PFC and HC components when involved in halogen bonded co-polymers as diagnostic probes of the interaction and as tools to rank the electron-donor ability of differently heteroatom substituted hydrocarbons.

A novel apparatus for joining carbon-carbon (C-C) composites is presented. This device was designed and built based on the concept of self-sustained oxygen-free high-temperature reactions. A layer of reactive mixture is contained between two disks of C-C composite that are to be joined. The stack is held in place between two electrodes, which are connected to a dc power supply. dc current is used to uniformly initiate the reaction in the reactive layer. The electrodes are also part of the pneumatic system, which applies a load to the stack. The designed hydraulic system is effective, lending to low cost and simplified, rapid, accurate operation. It provides a very short response time (˜10ms), which is important for the considered applications. All operational parameters such as initial and final loads, applied current, delay time between ignition and final load application, duration of Joule heating, and safety interlocks are controlled by a programable logic controller system. These features make it an efficient, user-friendly and safe machine to join refractory materials. The entire joining process takes place on the order of seconds, rather than hours as required for solid-state joining methods. The mechanical properties of the obtained joints are higher than those for the C-C composites.

Future space nuclear power systems will require radiator technology to dissipate excess heat created by a nuclear reactor. Large radiator fins with circulating coolant are in development for this purpose and an investigation of how to make them most efficient is underway. Maximizing the surface area while minimizing the mass of such radiator fins is critical for obtaining the highest efficiency in dissipating heat. Processes to develop surface roughness are under investigation to maximize the effective surface area of a radiator fin. Surface roughness is created through several methods including oxidation and texturing. The effects of atomic oxygen impingement on carbon-carbon surfaces are currently being investigated for texturing a radiator surface. Early studies of atomic oxygen impingement in low Earth orbit indicate significant texturing due to ram atomic oxygen. The surface morphology of the affected surfaces shows many microscopic cones and valleys which have been experimentally shown to increase radiation emittance. Further study of this morphology proceeded in the Long Duration Exposure Facility (LDEF). Atomic oxygen experiments on the LDEF successfully duplicated the results obtained from materials in spaceflight by subjecting samples to 4.5 eV atomic oxygen from a fixed ram angle. These experiments replicated the conical valley morphology that was seen on samples subjected to low Earth orbit.

A program of experiments and analysis was performed to examine failure criteria for 3-D carbon-carbon composites. Specimens from an FMI 2-2-1 weave and an AVCO 2-2-5 weave were investigated using off-axis tests in tension and compression. The stress strain responses were analyzed to provide composite stiffness and yield strength as a function of yarn angle. Estimates of the material shear stiffness were calculated. The data for yield strength versus yarn angle were fitted with Tsai-Hill and Tsai-Wu failure criteria. Values of the shear strength for yield and ultimate failure were found. The general off-axis nonlinear stress strain curves were condensed to a single equation using the theory of anisotropic plasticity. A simple criterion was found to predict the onset of yielding for 3-D weaves subjected to off-axis loading. Validation of the failure criteria and plasticity models was made by analyzing stress fields in the region of a hole and comparing with experimental data. Observations of microscopic material damage and failure surfaces were made for specimens subjected to on-axis compression and off-axis tension. The spread of damage in on-axis compression specimens is explained in detail.

Catalytic asymmetric conjugate addition reactions with organometallic reagents are powerful reactions in synthetic chemistry. Procedures that use non-stabilized carbanions have been developed extensively, but these suffer from a number of limitations that prevent their use in many situations. Here, we report that alkylmetal species generated in situ from alkenes can be used in highly enantioselective 1,4-addition initiated by a copper catalyst. Using alkenes as starting materials is desirable because they are readily available and have favourable properties when compared to pre-made organometallics. High levels of enantioselectivity are observed at room temperature in a range of solvents, and the reaction tolerates functional groups that are not compatible with comparable methods-a necessary prerequisite for efficient and protecting-group-free strategies for synthesis. PMID:22824897

Catalytic asymmetric conjugate addition reactions with organometallic reagents are powerful reactions in synthetic chemistry. Procedures that use non-stabilized carbanions have been developed extensively, but these suffer from a number of limitations that prevent their use in many situations. Here, we report that alkylmetal species generated in situ from alkenes can be used in highly enantioselective 1,4-addition initiated by a copper catalyst. Using alkenes as starting materials is desirable because they are readily available and have favourable properties when compared to pre-made organometallics. High levels of enantioselectivity are observed at room temperature in a range of solvents, and the reaction tolerates functional groups that are not compatible with comparable methods—a necessary prerequisite for efficient and protecting-group-free strategies for synthesis.

The broader impact of the proposed research goes beyond scientific curiosity. First, chemical technologies developed herein will significantly enhance the efficiency of chemical synthesis and reduce the amount of organic waste in reactions and product isolations by...

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Amorphous carbon (a-C) and several related materials (DLCs) may have ultralow friction coefficients that can be used for saving-energy applications. However, poor chemical bonding of a-C/DLC films on metallic alloys is expected, due to the stability of carbon-carbonbonds. Silicon-based intermediate layers are employed to enhance the adherence of a-C:H films on ferrous alloys, although the role of such buffer layers is not yet fully understood in chemical terms. The chemical bonding of a-C:H thin films on ferrous alloy intermediated by a nanometric SiCx:H buffer layer was analyzed by X-ray photoelectron spectroscopy (XPS). The chemical profile was inspected by glow discharge optical emission spectroscopy (GDOES), and the chemical structure was evaluated by Raman and Fourier transform infrared spectroscopy techniques. The nature of adhesion is discussed by analyzing the chemical bonding at the interfaces of the a-C:H/SiCx:H/ferrous alloy sandwich structure. The adhesion phenomenon is ascribed to specifically chemical bonding character at the buffer layer. Whereas carbon-carbon (C-C) and carbon-silicon (C-Si) bonds are formed at the outermost interface, the innermost interface is constituted mainly by silicon-iron (Si-Fe) bonds. The oxygen presence degrades the adhesion up to totally delaminate the a-C:H thin films. The SiCx:H deposition temperature determines the type of chemical bonding and the amount of oxygen contained in the buffer layer. PMID:26135943

Rapidly solidified alloys, based upon the Al-Fe-V-Si system and designed for elevated temperature applications, were evaluated for superplasticity and diffusion bonding behavior. Alloys with 8, 16, 27, and 36 volume percent silicide dispersoids were produced; dispersoid condition was varied by rolling at 300, 400, and 500 C (572, 752, and 932 F). Superplastic behavior was evaluated at strain rates from 1 x 10(exp -6)/s to 8.5/s at elevated temperatures. The results indicate that there was a significant increase in elongation at higher strain rates and at temperatures above 600 C (1112 F). However, the exposure of the alloys to temperatures greater than 600 C (1112 F) resulted in the coarsening of the strengthening dispersoid and the degradation of mechanical properties. Diffusion bonding was possible using low gas pressure at temperatures greater than 600 C (1112 F) which also resulted in degraded properties. The bonding of Al-Fe-V-Si alloys to 7475 aluminum alloy was performed at 516 C (960 F) without significant degradation in microstructure. Bond strengths equal to 90 percent that of the base metal shear strength were achieved. The mechanical properties and microstructural characteristics of the alloys were investigated.

Carbon-carbon composites are an attractive choice for fusion reactor plasma facing components because of their low atomic number, superior thermal shock resistance, and low neutron activation. Next generation tokamak reactors such as the International Thermonuclear Experimental Reactor (ITER), will require high thermal conductivity carbon-carbon composites and other materials, such as beryllium, to protect their plasma facing components from the anticipated high heat fluxes. Moreover, ignition machines such as ITER will produce a large neutron flux. Consequently, the influence of neutron damage on the structure and properties of carbon-carbon composite materials must be evaluated. Data from two irradiation experiments are reported and discussed here. Carbon-carbon composite materials were irradiated in target capsules in the High Flux Isotope Reactor (HAIR) at Oak Ridge National Laboratory (ORAL). A peak damage dose of 4.7 displacements per atom (da) at an irradiation temperature of {approximately}600{degrees}C was attained. The carbon materials irradiated here included unidirectional, two- directional, and three-directional carbon-carbon composites. Irradiation induced dimensional changes are reported for the materials and related to single crystal dimensional changes through fiber and composite structural models. Moreover, carbon-carbon composite material dimensional changes are discussed in terms of their architecture, fiber type, and graphitization temperature. Neutron irradiation induced reductions in the thermal conductivity of two, three-directional carbon-carbon composites are reported, and the recovery of thermal conductivity due to thermal annealing is demonstrated. Irradiation induced strength changes are reported for several carbon-carbon composite materials and are explained in terms of in-crystal and composite structural effects.

The radical S-adenosylmethionine (SAM) protein PqqE is predicted to function in the pyrroloquinoline quinone (PQQ) biosynthetic pathway via catalysis of carbon-carbonbond formation between a glutamate and tyrosine side chain within the small peptide substrate PqqA. We report here that PqqE activity is dependent on the accessory protein PqqD, which was recently shown to bind PqqA tightly. In addition, PqqE activity in vitro requires the presence of a flavodoxin- and flavodoxin reductase-based reduction system, with other reductants leading to an uncoupled cleavage of the co-substrate SAM. These results indicate that PqqE, in conjunction with PqqD, carries out the first step in PQQ biosynthesis: a radical-mediated formation of a new carbon-carbonbond between two amino acid side chains on PqqA. PMID:26961875

A comparison of specific strengths of candidate high-temperature materials as a function of temperature is shown. From this comparison, it is apparent why there is an interest in carbon-carbon composites for applications as a strong, light-weight thermal protection system (TPS), or as hot structure, for applications above 2500 F. The lower bound of the carbon-carbon band is representative of the tensile strength of cross-ply Advanced Carbon-Carbon (ACC). The upper bound represents capabilities of various experimental carbon-carbon composites. Thin carbon-carbon composites, such as would be used as TPS panels or hot aero-structure, are usually constructed of layups of 2-D fabrics of carbon-fiber yarns (tows). Although the in-plane strengths of these composites can be very attractive, a major problem area is low interlaminar strength. The low interlaminar strength is the result of a relatively weak carbon matrix and poor interaction between the fibers and matrix. The purpose of this paper is to discuss strategies being employed to improve the interlaminar strengths of the materials at the upper bound of the carbon-carbon band, and to present some recent encouraging results. The emphasis of these strategies is to improve interlaminar shear and tensile strengths while maintaining, or even improving, the inplane properties.

The photo- and electroluminescence spectra of silicon-based structures formed by direct bonding with simultaneous doping with rare-earth metals are studied. It is shown that emission in the visible and IR spectral ranges can be obtained from n-Si:Er/p-Si and n-Si:Eu/p-Si structures fabricated by the method suggested in the study. The results obtained make this method promising for the fabrication of optoelectronic devices.

Polyynes, the smaller analogues of one dimensional infinite chain carbon allotrope carbyne, have been studied for the type and strength of the intermolecular interactions in their dimer and tetramer complexes using density functional theory. The nature of end group functionalities and the chain length of the polyynes are varied to assess their role in modulating the non-covalent interaction energy. As seen in molecular electrostatic potential analysis, all the polyyne complexes showed a multitude of non-covalent CC interactions, resulting from complementary electrostatic interactions between relatively electron rich formal triple bond region of one monomer and the electron deficient formal single bond region of the other monomer. This type of paired (C[triple bond, length as m-dash]C)(C-C) bonding interaction, also characterized using quantum theory of atoms-in-molecules, increases with increase in the monomer chain length leading to substantial increase in interaction energy (Eint); -1.07 kcal mol(-1) for the acetylene dimer to -45.83 kcal mol(-1) for the 50yne dimer. The magnitude of Eint increases with substitutions at end positions of the polyyne and this effect persists even up to 50 triple bonds, the largest chain length analyzed in this paper. The role of CC interactions in stabilizing the polyyne dimers is also shown by sliding one monomer in a dimer over the other, which resulted in multiple minima with a reduced number of CC interactions and lower values of Eint. Furthermore, strong cooperativity in the CC bond strength in tetramers is observed as the interaction energy per monomer (Em) of the polyyne is 2.5-2.8 times higher compared to that of the dimer in a test set of four tetramers. The huge gain in energy observed in large polyyene dimers and tetramers predicts the formation of polyyne bundles which may find use in the design of new functional molecular materials. PMID:26412713

Carbon-carbon composite materials offer greater thermal efficiency, stiffness to weight ratio, tailorability, and dimensional stability than aluminum. These lightweight thermal materials could significantly reduce the overall costs associated with satellite thermal control and weight. However, the high cost and long lead-time for carbon-carbon manufacture have limited their widespread usage. Consequently, an informal partnership between government and industrial personnel called the Carbon-Carbon Spacecraft Radiator Partnership (CSRP) was created to foster carbon-carbon composite use for thermally and structurally demanding space radiator applications. The first CSRP flight opportunity is on the New Millennium Program (NMP) Earth Orbiter-1 (EO-1) spacecraft, scheduled for launch in late 1999. For EO-1, the CSRP designed and fabricated a Carbon-Carbon Radiator (CCR) with carbon-carbon facesheets and aluminum honeycomb core, which will also serve as a structural shear panel. While carbon-carbon is an ideal thermal candidate for spacecraft radiators, in practice there are technical challenges that may compromise performance. In this work, the thermal and mechanical performance of the EO-1 CCR is assessed by analysis and testing. Both then-nal and mechanical analyses were conducted to predict the radiator response to anticipated launch and on-orbit loads. The thermal model developed was based on thermal balance test conditions. The thermal analysis was performed using SINDA version 4.0. Structural finite element modeling and analysis were performed using SDRC/1-DEAS and UAI/NASTRAN, respectively. In addition, the CCR was subjected to flight qualification thermal/vacuum and vibration tests. The panel meets or exceeds the requirements for space flight and demonstrates promise for future satellite missions.

Carbon-carbon composites increasingly are being used for plasma-facing component (PFC) applications in magnetic-confinement plasma-fusion devices. They offer substantial advantages such as enhanced physical and mechanical properties and superior thermal shock resistance compared to the previously favored bulk graphite. Next-generation plasma-fusion reactors, such as the International Thermonuclear Experimental Reactor (ITER) and the Burning Plasma Experiment (BPX), will require advanced carbon-carbon composites possessing extremely high thermal conductivity to manage the anticipated extreme thermal heat loads. This report outlines a program that will facilitate the development of advanced carbon-carbon composites specifically tailored to meet the requirements of ITER and BPX. A strategy for developing the necessary associated design data base is described. Materials property needs, i.e., high thermal conductivity, radiation stability, tritium retention, etc., are assessed and prioritized through a systems analysis of the functional, operational, and component requirements for plasma-facing applications. The current Department of Energy (DOE) Office of Fusion Energy Program on carbon-carbon composites is summarized. Realistic property goals are set based upon our current understanding. The architectures of candidate PFC carbon-carbon composite materials are outlined, and architectural features considered desirable for maximum irradiation stability are described. The European and Japanese carbon-carbon composite development and irradiation programs are described. The Working Group conclusions and recommendations are listed. It is recommended that developmental carbon-carbon composite materials from the commercial sector be procured via request for proposal/request for quotation (RFP/RFQ) as soon as possible.

The wing leading edge and nose cone of the Space Shuttle are fabricated from a reinforced carbon/carbon material (RCC). The material attains its oxidation resistance from a diffusion coating of SiC and a glass sealant. During re-entry, the RCC material is subjected to an oxidizing high temperature environment, which leads to degradation via several mechanisms. These mechanisms include oxidation to form a silica scale, reaction of the SiO2 with the SiC to evolve gaseous products, viscous flow of the glass, and vaporization of the glass. Each of these is discussed in detail. Following extended service and many missions, the leading-edge wing surfaces have exhibited small pinholes. A chloridation/oxidation mechanism is proposed to arise from the NaCl deposited on the wings from the sea-salt laden air in Florida. This involves a local chloridation reaction of the SiC and subsequent re-oxidation at the external surface. Thermodynamic calculations indicate the feasibility of these reactions at active pits. Kinetic calculations predict pore depths close to those observed.

As the terminal step in photosystem II, and a potential half-reaction for artificial photosynthesis, water oxidation (2H2O → O2 + 4e- + 4H+) is key, but it imposes a significant mechanistic challenge with requirements for both 4e-/4H- loss and O—O bond formation. Significant progress in water oxidation catalysis has been achieved recently by use of single-site Ru metal complex catalysts such as [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine]. When oxidized from RuII-OH22+ to RuV = O3+, these complexes undergo O—O bond formation by O-atom attack on a H2O molecule, which is often the rate-limiting step. Microscopic details of O—O bond formation have been explored by quantum mechanical/molecular mechanical (QM/MM) simulations the results of which provide detailed insight into mechanism and a strategy for enhancing catalytic rates. It utilizes added bases as proton acceptors and concerted atom–proton transfer (APT) with O-atom transfer to the O atom of a water molecule in concert with proton transfer to the base (B). Base catalyzed APT reactivity in water oxidation is observed both in solution and on the surfaces of oxide electrodes derivatized by attached phosphonated metal complex catalysts. These results have important implications for catalytic, electrocatalytic, and photoelectrocatalytic water oxidation.

Today, research is increasingly focused on surface control of semiconductors; however, very little is known about the effect of bulk chemical bonds on photoelectrochemistry properties. In this report, Bi2O(OH)2SO4 with and without specific Bi-O-S bonds (WB and WOB) is synthesized via hydrothermal and water bath methods, respectively, and we reveal the Bi-O-S bond-dependent photoelectrochemistry properties. Both WB and WOB belong to a monoclinic space group (P21/c), but the newly synthesized WB has different unit cell parameters of a = 8.062 Å, b = 8.384 Å, and c = 5.881 Å, compared with WOB (a = 7.692(3) Å, b = 13.87(1) Å, c = 5.688(2) Å). Compared with WOB (4.18 eV), WB has a narrower band gap (3.6 eV), higher electrical conductivity, and an increased charge separation efficiency. It is found that the electrons are easy to transfer along the newly formed Bi-O-S bond in bulk; thus, the Bi-O-S bonds in WB have efficiently improved the photoelectrochemistry properties. As a result, WB exhibits a 1.1 times higher photocatalytic activity than WOB for the degradation of RhB under ultraviolet light irradiation (<420 nm). This helps us to understand the photoelectrochemistry properties from crystal bulk, but not merely from the crystal surface; thus, this study provides a new idea for improved photoelectrochemistry properties of semiconductors. PMID:27070507

We fabricated a two-color surface emitting device of a coupled cavity structure, which is applicable to terahertz light source. GaAs/AlGaAs vertical multilayer cavity structures were grown on (001) and (113)B GaAs substrates and the coupled multilayer cavity structure was fabricated by wafer bonding them. The top cavity contains self-assembled InAs quantum dots (QDs) as optical gain materials for two-color emission of cavity-mode lights. The bonding position was optimized for the equivalent intensity of two-color emission. We formed a current injection structure, and two-color emission was observed by current injection, although no lasing was observed.

Primary alcohols have been an active area of research since the beginning of the 20th century. The main problem in studying monohydroxy alcohols is the molecular origin of the slower Debye relaxation, whereas the faster process, recognized as structural relaxation, remains much less investigated. This is because in many primary alcohols the structural process is strongly overlapped by the dominating Debye relaxation. Additionally, there is still no answer for many fundamental questions concerning the origin of the molecular characteristic properties of these materials. One of them is the role of molecular architecture in the formation of hydrogen-bonded structures and its potential connection to the relaxation dynamics of Debye and structural relaxation processes. In this article, we present the results of ambient and high-pressure dielectric studies of monohydroxy alcohols with similar chemical structures but different carbon chain lengths (2-ethyl-1-butanol and 2-ethyl-1-hexanol) and positions of the OH- group (2-methyl-2-hexanol and 2-methyl-3-hexanol). New data are compared with previously collected results for 5-methyl-2-hexanol. We note that differences in molecular architecture have a significant influence on the formation of hydrogen-bonded structures, which is reflected in the behavior of the Debye and structural relaxation processes. Intriguingly, studying the relaxation dynamics in monohydroxy alcohols at high pressures of up to p = 1700 MPa delivers a fundamental bridge to understand the potential connection between molecular conformation and its response to the characteristic properties of these materials. PMID:27254726

A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

The synthesis of diarylpalladium(II) complexes by twofold aryl C-H bond activation was developed. These intermediates of oxidative cyclization reactions are stabilized by chelation with acetyl groups while still maintaining sufficient reactivity to study their reductive elimination. Four distinct triggers were found for the reductive elimination of these complexes to dibenzofurans and carbazoles. Thermal elimination occurs at very high temperatures, whereas ligand-promoted and oxidatively induced reductive eliminations proceed readily at room temperature. Under these conditions, no isomerization occurs. In contrast, weak Brønsted acids, such as acetic acid, lead to a sequence of proto-demetalation, isomerization to a κ(3) -diarylpalladium(II) complex, and reductive elimination to non-symmetrical cyclization products. PMID:27309346

The dynamics of protons in a one-dimensional hydrogen-bonded (HB) polypeptide chain (PC) is investigated theoretically. A new Hamiltonian is formulated with the inclusion of higher-order molecular interactions between peptide groups (PGs). The wave function of the excitation state of a single particle is replaced by a new wave function of a two-quanta quasi-coherent state. The dynamics is governed by a higher-order nonlinear Schrödinger equation and the energy transport is performed by the proton soliton. A nonlinear multiple-scale perturbation analysis has been performed and the evolution of soliton parameters such as velocity and amplitude is explored numerically. The proton soliton is thermally stable and very robust against these perturbations. The energy transport by the proton soliton is more appropriate to understand the mechanism of energy transfer in biological processes such as muscle contraction, DNA replication, and neuro-electric pulse transfer on biomembranes. PMID:26198375

Results of reactions of Na-K alloy in the solvent system glyme-triglyme on a series of compounds, bibenzyl, 1,2-diphenylpropane, diphenylmethane, and phenyl-p-tolylmethane, to determine whether the Birch-Hueckel reduction could be used in this solvent system to cleave C-C bonds are reported. Both methyl-/sup 14/C iodide and water were studied as quenchers, and the products from all reactions were analyzed by gas chromatography. The results indicated that coal can be efficiently degraded at low-temperatures by cleavage of aliphatic as well as aromatic-aliphatic C-C bonds by the action of Na-K alloy under conditions studied in this work. (BLM)

The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

The quality of water is continuously deteriorating due to its increasing toxic threat to humans and the environment. It is imperative to perform treatment of wastewater in order to remove pollutants and to get good quality water. Carbon materials like porous carbon, carbon nanotubes and fullerene have been extensively used for advanced treatment of wastewaters. In recent years, carbon nanomaterials have become promising adsorbents for water treatment. This review attempts to compile relevant knowledge about the adsorption activities of porous carbon, carbon nanotubes and fullerene related to various organic and inorganic pollutants from aqueous solutions. A detailed description of the preparation and treatment methods of porous carbon, carbon nanotubes and fullerene along with relevant applications and regeneration is also included. PMID:23430732

Co-crystallisation of, in particular, 4-iodotetrafluorophenol with a series of secondary and tertiary cyclic amines results in deprotonation of the phenol and formation of the corresponding ammonium phenate. Careful examination of the X-ray single-crystal structures shows that the phenate anion develops a C=O double bond and that the C–C bond lengths in the ring suggest a Meissenheimer-like delocalisation. This delocalisation is supported by the geometry of the phenate anion optimised at the MP2(Full) level of theory within the aug-cc-pVDZ basis (aug-cc-pVDZ-PP on I) and by natural bond orbital (NBO) analyses. With sp2 hybridisation at the phenate oxygen atom, there is strong preference for the formation of two non-covalent interactions with the oxygen sp2 lone pairs and, in the case of secondary amines, this occurs through hydrogen bonding to the ammonium hydrogen atoms. However, where tertiary amines are concerned, there are insufficient hydrogen atoms available and so an electrophilic iodine atom from a neighbouring 4-iodotetrafluorophenate group forms an I⋅⋅⋅O halogen bond to give the second interaction. However, in some co-crystals with secondary amines, it is also found that in addition to the two hydrogen bondsforming with the phenate oxygen sp2 lone pairs, there is an additional intermolecular I⋅⋅⋅O halogen bond in which the electrophilic iodine atom interacts with the C=O π-system. All attempts to reproduce this behaviour with 4-bromotetrafluorophenol were unsuccessful. These structural motifs are significant as they reproduce extremely well, in low-molar-mass synthetic systems, motifs found by Ho and co-workers when examining halogen-bonding interactions in biological systems. The analogy is cemented through the structures of co-crystals of 1,4-diiodotetrafluorobenzene with acetamide and with N-methylbenzamide, which, as designed models, demonstrate the orthogonality of hydrogen and halogen bonding proposed in Ho’s biological study. PMID

The oxidation of SiC-protected carbon/carbon through machined slots and naturally occurring craze cracks in the SiC was studied. The slot and crack geometries were characterized, and the subsurface oxidation of the carbon/carbon substrate at temperatures of 1000 to 1300 C in air was assessed using weight change, x-ray computed tomography, and optical microscopy of sections. Rate constants were derived from these measurements and compared with a two-step diffusion control model of carbon oxidation. Oxidation kinetic measurements on both the specimens with machined slots and with naturally occurring craze cracks showed good agreement with the model.

The oxidation of SiC-protected carbon/carbon through machined slots and naturally occurring craze cracks in the SiC was studied. The slot and crack geometries were characterized, and the subsurface oxidation of the carbon/carbon substrate at temperatures of 1000 to 1300 C in air was assessed using weight change, x-ray computed tomography, and optical microscopy of sections. Rate constants were derived from these measurements and compared with a two-step diffusion control model of carbon oxidation. Oxidation kinetic measurements on both the specimens with machined slots and with naturally occurring craze cracks showed good agreement with the model.

An improved. lightweight, turbine housing unit for an intermittent combustion reciprocating internal combustion engine turbocharger is prepared from a lay-up or molding of carbon-carbon composite materials in a single-piece or two-piece process. When compared to conventional steel or cast iron, the use of carbon-carbon composite materials in a turbine housing unit reduces the overall weight of the engine and reduces the heat energy loss used in the turbo-charging process. This reduction in heat energy loss and weight reduction provides for more efficient engine operation.

The He I photoelectron spectra of M{sub 2}(form){sub 4}(M = Cr, Mo, W; form - N,N{prime}-diphenylformamidinate) and Mo{sub 2}(cyform){sub 4} (cyform = N,N{prime}-dicyclohexylformamidinate) are presented. For comparison, the Ne I, He I, and He II photoelectron spectra of Mo{sub 2}(p-CH{sub 3}-form){sub 4} have also been obtained. The valence ionization features of these molecules are interpreted based on (1) the changes that occur with the metal and ligand substitutions, (2) the changes in photoelectron cross sections with excitation source, and (3) the changes from previously studied dimetal complexes. These photoelectron spectra are useful for revealing the effects that better electron donor ligands have on the valence electronic structure of M{sub 2}(L-L){sub 4} systems. Comparison with the He I spectra of the isoelectronic M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} compounds is particularly revealing. Unlike with the more electron-withdrawing acetate ligand, several formamidinate-based ionizations derived from the nitrogen p{sub {pi}} orbitals occur among the metal-metal {sigma}, {pi}, and {delta} ionization bands. Although these formamidinate-based levels are close in energy to the occupied metal-metal bonds, they have little direct mixing interaction with them. The shift of the metal-metal bond ionizations to lower ionization energies for the formamidinate systems is primarily a consequence of the lower electronegativity of the ligand and the better {pi} donation into empty metal levels. The metal-metal {delta} orbital experiences some additional net bonding interaction with ligand orbitals of the same symmetry. Also, an additional bonding interaction from ligand-to-metal electron donation to the {delta}* orbital is identified. These spectra suggest a greater degree of metal-ligand covalency than in the related M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} systems. Fenske-Hall molecular orbital and density functional (ADF) calculations agree with the assignment and

The disadvantages of carbon-carbon composites, in addition to the oxidation problem, are low thermal expansion, expensive fabrication procedures, and poor off axis properties. The background of carbon-carbon composites, their fabrication, oxidation, oxidation protection and mechanical testing in flexure are discussed.

This paper examines first some basic aspects critical to the analysis of Volatile Sulfur Compounds (VSCs), such as the analytical characteristics of the GC-pFPD system and the stability of the different standard solutions required for a proper calibration. Following, a direct static headspace analytical method for the determination of exclusively free forms of VSCs has been developed. Method repeatability is better than 4%, detection limits for main analytes are below 0.5μgL(-1), and the method dynamic linear range (r(2)>0.99) is expanded by controlling the split ratio in the chromatographic inlet to cover the natural range of occurrence of these compounds in wines. The method gives reliable estimates of headspace concentrations but, as expected, suffers from strong matrix effects with recoveries ranging from 0 to 100% or from 60 to 100 in the cases of H2S and the other mercaptans, respectively. This demonstrates the existence of strong interactions of these compounds with different matrix components. The complexing ability of Cu(2+) and to a lower extent Fe(2+) and Zn(2+) has been experimentally checked. A previously developed method in which the wine is strongly diluted with brine and the volatiles are preconcentrated by HS-SPME, was found to give a reliable estimation of the total amount (free+complexed) of mercaptans, demonstrating that metal-mercaptan complexes are reversible. The comparative analysis of different wines by the two procedures reveals that in normal wines H2S and methanethiol can be complexed at levels above 99%, with averages around 97% for H2S and 75% for methanethiol, while thioethers such as dimethyl sulfide (DMS) are not complexed. Overall, the proposed strategy may be generalized to understand problems caused by VSCs in different matrices. PMID:25064535

Carbon-carbon composites and carbon-polyimide composites are being considered for space radiator applications owing to their light weight and high thermal conductivity. For those radiator applications where sunlight will impinge on the surface, it will be necessary to apply a white thermal control paint to minimize solar absorptance and enhance infrared emittance. Several currently available white thermal control paints were applied to candidate carbon-carbon and carbon-polyimide composites and were subjected to vacuum thermal cycling in the range of -100 C to +277 C. The optical properties of solar absorptance and infrared emittance were evaluated before and after thermal cycling. In addition, adhesion of the paints was evaluated utilizing a tape test. The test matrix included three composites: resin-derived carbon-carbon and vapor infiltrated carbon-carbon, both reinforced with pitch-based P-120 graphite fibers, and a polyimide composite reinforced with T-650 carbon fibers, and three commercially available white thermal control paints: AZ-93, Z-93-C55, and YB-71P.

Using the Weizsacher-Williams method of virtual quanta, total cross section estimates for the photoproduction of neutral subthreshold pins in carbon-carbon collisions at incident energies below 300 MeV/nucleon are made. Comparisons with recent experimental data indicate that the photoproduction mechanism makes an insignificant contribution to these measured cross sections.

Advanced thermal protection materials envisioned for use on future hypersonic vehicles will likely be subjected to temperatures in excess of 1811 K (2800 F) and, therefore, will require the rapid conduction of heat away from the stagnation regions of wing leading edges, the nose cap area, and from engine inlet and exhaust areas. Carbon-carbon composite materials are candidates for use in advanced thermal protection systems. For design purposes, high temperature thermophysical property data are required, but a search of the literature found little thermal conductivity data for carbon-carbon materials above 1255 K (1800 F). Because a need was recognized for in-plane and through-the-thickness thermal conductivity data for carbon-carbon composite materials over a wide temperature range, Langley Research Center (LaRC) embarked on an effort to compile a consistent set of thermal conductivity values from room temperature to 1922 K (3000 F) for carbon-carbon composite materials on hand at LaRC for which the precursor materials and thermal processing history were known. This report documents the thermal conductivity data generated for these materials. In-plane thermal conductivity values range from 10 to 233 W/m-K, whereas through-the-thickness values range from 2 to 21 W/m-K.

CO binding kinetics to the homodimeric myoglobin (Mb) from Nassa mutabilis has been investigated between pH 1.9 and 7.0. Protonation of the proximal imidazole at low pH (less than or equal to 3.0) and the consequent cleavage of the HisF8NE2-Fe proximal bond brings about a approximately 20-fold increase of the second-order rate constant for CO binding. This process displays a pKa = 4.0 +/- 0.2, significantly higher than that observed in all other deoxygenated hemoproteins investigated up to now. Such a feature underlies a decreased energy for the HisF8NE2-Fe proximal bond in the unliganded form and it also appears supported by resonance Raman spectroscopy in the low frequency region of the Fe(II) deoxygenated hemoprotein. Further, the pH-rate profile of N. mutabilis Mb, like that of the homodimeric hemoglobin (Hb) from Scapharca inaequivalvis (Coletta, M., Boffi, A., Ascenzi, P., Brunori, M. and Chiancone, E. (1990) J. Biol. Chem. 265, 4828-4830), can be described only by assuming a concerted proton-linked transition with n = 1.8 +/- 0.1. Such a characteristic suggests, also on the basis of the amino acid sequence homology between N. mutabilis Mb and S. inaequivalvis Hb in the region forming the subunit interface, that the interaction mechanism is similar for the two homodimeric proteins, and drastically different Hb in the region forming the subunit interface, that the interaction mechanism is similar for the two homodimeric proteins, and drastically different from that operative in other hemoproteins. PMID:1733775

Daily concentrations of carbonatecarbon (CC) in PM 2.5 collected in semi-arid area in Northeast China (Tongyu) were quantified by acidification that measures carbon dioxide (CO 2) gas evolved using DRI Model 2001 Thermal Optical reflectance (TOR) Carbon Analyzer. The concentrations of CC during Asian dust storm (DS) and non-dust storm (NDS) periods during 14 April to 21 June, 2006 were determined and the transport pathways and possible sources for the CO 32- aerosols were identified. Concentrations of CC in PM 2.5 collected from 14 April to 23 June, 2006 in Tongyu are ranged from 0.1 to 7.5 μgC m -3 with an average of 1.3 μgC m -3. The average CC concentration during DS events was 2.6 ± 1.7 μg m -3, which was almost 4 times the daily average concentration of 0.6 ± 0.5 μg m -3 during non-dust storm (NDS) period. Carbonatecarbon accounted for 10% and 4% of total carbon in Tongyu during DS and NDS period, respectively. Carbonate concentrations were also derived by calculating the difference between cations and anions (ionic balance method). And good correlation is observed for the carbonate measured to the values for carbonate calculated from the ionic balance difference ( R2 = 0.90). Higher correlations were observed between Ca with selected water-soluble ions (sulfate, nitrate or chloride) and elemental carbon in DS than in NDS periods. This is consistent with previous studies that more calcium salts (sulfate, nitrate or chloride) were formed during atmospheric transport during DS period. During the DS in spring 2006, three groups (A to C) of air mass trajectories were identified that passed over Tongyu. In general, when the air mass came from northwest, and south or southwest to Tongyu, high concentrations of carbonate were observed.

Vinyl-terminated self-assembled monolayers (SAMs) on silicon oxide substrates were chemically modified by the addition of a bis(trifluoromethyl)methylene group in a rare gas-phase C–C bond-forming reaction to directly generate films carrying terminal CF3 groups. The vinyl-terminated films were treated with hexafluoroacetone azine (HFAA) for modification. The films were characterized with ellipsometry, contact angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). In this study, we find that for optimized conditions clean reactions occur on a surface between SAMs with terminal olefins and HFAA, and the product is consistent with bis(trifluoromethyl)cyclopropanation formation after nitrogen extrusion. PMID:24806554

Vinyl-terminated self-assembled monolayers (SAMs) on silicon oxide substrates were chemically modified by the addition of a bis(trifluoromethyl)methylene group in a rare gas-phase C-C bond-forming reaction to directly generate films carrying terminal CF3 groups. The vinyl-terminated films were treated with hexafluoroacetone azine (HFAA) for modification. The films were characterized with ellipsometry, contact angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). In this study, we find that for optimized conditions clean reactions occur on a surface between SAMs with terminal olefins and HFAA, and the product is consistent with bis(trifluoromethyl)cyclopropanation formation after nitrogen extrusion. PMID:24806554

OAK-B135 Carbon monoxide dehydrogenase from Moorella thermoacetica catalyzes the reversible oxidation of CO to CO2 at a nickel-iron-sulfur active-site called the C-cluster. Mutants of a proposed proton transfer pathway and of a cysteine residue recently found to form a persulfide bond with the C-cluster were characterized. Four semi-conserved histidine residues were individually mutated to alanine. His116 and His122 were essential to catalysis, while His113 and His119 attenuated catalysis but were not essential. Significant activity was ''rescued'' by a double mutant where His116 was replaced by Ala and His was also introduced at position 115. Activity was also rescued in double mutants where His122 was replaced by Ala and His was simultaneously introduced at either position 121 or 123. Activity was also ''rescued'' by replacing His with Cys at position 116. Mutation of conserved Lys587 near the C-cluster attenuated activity but did not eliminate it. Activity was virtually abolished in a double mutant where Lys587 and His113 were both changed to Ala. Mutations of conserved Asn284 also attenuated activity. These effects suggest the presence of a network of amino acid residues responsible for proton transfer rather than a single linear pathway. The Ser mutant of the persulfide-forming Cys316 was essentially inactive and displayed no EPR signals originating from the C-cluster. Electronic absorption and metal analysis suggests that the C-cluster is absent in this mutant. The persulfide bond appears to be essential for either the assembly or stability of the C-cluster, and/or for eliciting the redox chemistry of the C-cluster required for catalytic activity.

The conformational properties in vacuo and in solution of N-protonated dopamine have been studied making use of ab initio SCF calculations in vacuo and free energy calculations in aqueous solution, in the framework of the polarizable continuum model (PCM), on the STO-3G, 4-31G and 6-31G ∗ optimized geometries obtained in vacuo. The in vacuo energy profiles along a few sections of the potential energy surface turn out to be very close for the extended basis sets, while the STO-3G eresults are slightly dispalced. The largest difference between the minimal and the extended basis sets is found for the perpendicular arrangement, which is however the lowest energy profile with low barriers to the CCCN rotation both invacuo and in solution. The solvent stabilizes the trans over the gauche rotamers. Teh conformers without intramolecular H-bond between the -OH side chains are favored by the solvent, which makes the planar i, anti conformers as stable as the corresponding conformers with an intramolecular H-bond in aqueous solution. The solvation free energy is considerably less basis set dependent than the potential energy in vacuo. The ab initio PCM results slightly favor the planar 1 form over the planar 2 form whereas the semiempirical AMSOL results of Urban, Cramer and Famini (J. Am. Chem. Soc. 114 (1992) 8226) do the opposite. The cavitation free energy is nearly independent of the basis set. The almost constant (about 4.4 kcal/mol) cavitation and dispersion-repulsion corrections do not affect the differential quantities.

Report presents data on physical properties of carbon-fiber-reinforced carbon-matrix and phenolic-matrix composite materials. Based on tests conducted on panels, cylinders, blocks, and formed parts. Data used by designers to analyze thermal-response and stress levels and develop structural systems ensuring high reliability at minimum weight.

New carbon-nitrogen bonds were formed on addition of isocyanide and ketone reagents to the oxonitride species [{Ti(η(5)-C5Me5)(μ-O)}3(μ3-N)] (1). Reaction of 1 with XylNC (Xyl = 2,6-Me2C6H3) in a 1:3 molar ratio at room temperature leads to compound [{Ti(η(5)-C5Me5)(μ-O)}3(μ-XylNCCNXyl)(NCNXyl)] (2), after the addition of the nitrido group to one coordinated isocyanide and the carbon-carbon coupling of the other two isocyanide molecules have taken place. Thermolysis of 2 gives [{Ti(η(5)-C5Me5)(μ-O)}3(XylNCNXyl)(CN)] (3) where the heterocumulene [XylNCCNXyl] moiety and the carbodiimido [NCNXyl] fragment in 2 have undergone net transformations. Similarly, tert-butyl isocyanide (tBuNC) reacts with the starting material 1 under mild conditions to give the paramagnetic derivative [{Ti3(η(5)-C5Me5)3(μ-O)3(NCNtBu)}2(μ-CN)2] (4). However, compound 1 provides the oxo ketimide derivatives [{Ti3(η(5)-C5Me5)3(μ-O)4}(NCRPh)] [R = Ph (5), p-Me(C6H4) (6), o-Me(C6H4) (7)] upon reaction with benzophenone, p-methylbenzophenone, and o-methylbenzophenone, respectively. In these reactions, the carbon-oxygen double bond is completely ruptured, leading to the formation of a carbon-nitrogen and two metal-oxygen bonds. The molecular structures of complexes 2-4, 6, and 7 were determined by single-crystal X-ray diffraction analyses. Density functional theory calculations were performed on the incorporation of isocyanides and ketones to the model complex [{Ti(η(5)-C5H5)(μ-O)}3(μ3-N)] (1H). The mechanism involves the coordination of the substrates to one of the titanium metal centers, followed by an isomerization to place those substrates cis with respect to the apical nitrogen of 1H, where carbon-nitrogen bond formation occurs with a low-energy barrier. In the case of aryl isocyanides, the resulting complex incorporates additional isocyanide molecules leading to a carbon-carbon coupling. With ketones, the high oxophilicity of titanium promotes the unusual total cleavage of the

The F(δ-)···F(δ-) intermolecular synthon was recently observed to be useful for generating a two-dimensional layered supramolecular architecture on the Ag(111) surface (Kawai, et al., ACS Nano, 2015). This was formed when the entirely negative covalently bonded fluorine atoms in phenyleneethynylene(bis(2,3,5,6-tetrafluoro-4-(2,3,4,5,6-pentafluorophenylethynyl)phenyl)-ethyne (BPEPE-F18)) were in close proximity to the same atoms in another BPEPE-F18 molecule. With a view to provide rigorous insights into the physical chemistry of such an intermolecular synthon, we have selected perfluorobenzene (C6F6) as a model compound, and have performed extensive DFT-M06-2X/6-311++G(d,p) investigations on a number of its homomolecular dimers, trimers, and tetramers. Of the twelve (C6F6)2 dimers investigated, a displaced-parallel arrangement with an uncorrected binding energy (ΔE) of -7.4 kcal mol(-1) was found to be the most stable, and an incorporation of the basis set superposition error (BSSE) has significantly reduced its ΔE to -4.7 kcal mol(-1). Besides, the ΔE for a minimum-energy least stable conformation of the same dimer, which involves a single σhole(-)···σhole(-) type F(δ-)···F(δ-) intermolecular bonding interaction, amounts to -0.62 and -0.24 kcal mol(-1) without and with BSSE, respectively. The geometry of another conformation of the dimer, which accompanies a set of three F(δ-)···F(δ-) intermolecular interactions somehow similarly to those observed in the layered supramolecular structure formed by the BPEPE-F18 molecules, lies at a relative energy of 6.5 kcal mol(-1) above the most stable conformation. Passing from the latter dimer to an analogous (C6F6)3 trimer, as well as from the trimer to an analogous (C6F6)4 tetramer, the latter two clusters comprising windmill-type F(δ-)···F(δ-) intermolecular topologies, we have marked a preferential increase in the value of ΔE from -0.94 (dimer) to -2.76 (trimer) to -4.49 kcal mol(-1) (tetramer

The out-of-plane fracture of a 2-D carbon-carbon composite was observed and characterized to gain an understanding of the factors influencing the stress distribution in such a laminate. Finite element analyses of a two-ply carbon-carbon composite under in-plane, out-of-plane, and thermal loading were performed. Under in-plane loading all components of stress were strong functions of geometry. Additionally, large thermal stresses were predicted. Out-of-plane tensile tests revealed that failure was interlaminar, and that cracks propagated along the fiber-matrix interface. An elasticity solution was utilized to analyze an orthotropic fiber in an isotropic matrix under uniform thermal load. The analysis reveals that the stress distributions in a transversely orthotropic fiber are radically different than those predicted assuming the fiber to be transversely isotropic.

The possible erosion of a carbon/carbon thermal shield by solar wind-charged particle radiation is reviewed. The present knowledge of erosion data for carbon and/or graphite is surveyed, and an explanation of erosion mechanisms under different charged particle environments is discussed. The highest erosion is expected at four solar radii. Erosion rates are analytically estimated under several conservative assumptions for a normal quiet and worst case solar wind storm conditions. Mass loss analyses and comparison studies surprisingly indicate that the predicted erosion rate by solar wind could be greater than by nominal free sublimation during solar wind storm conditions at four solar radii. The predicted overall mass loss of a carbon/carbon shield material during the critical four solar radii flyby can still meet the mass loss mission requirement of less than 0.0025 g/sec.

A data base program to generate statistically significant material-property data for carbon-carbon and carbon phenolic materials to be used in designs of Space Shuttle is described. The program, which will provide data necessary for thermal and stress modeling of Shuttle nozzle and exit cone structures, includes evaluation of tension, compression, shear strength, shear modulus, thermal expansion, thermal conductivity, permeability, and emittance for both materials; the testing of carbon phenolic materials also includes CTE, off-gassing, pyrolysis, and RTG. Materials to be tested will be excised from Space Shuttle inlet, throat, and exit cone billets and modified involute carbon-carbon exit cones; coprocessed blocks, panels, and cylinders will also be tested.

The kinetic peculiarities of diamond crystallization in multicomponent K-Na-Mg-Ca-carbonate-carbon system have been studied in conditions of diamond stability at 1500-1800°C and 7.5-8.5 GPa. It has been established that the diamond phase nucleation density at a fixed temperature of 1600°C decreases from 1.3 × 105 nuclei/mm3 at 8.5 GPa to 3.7 × 103 nuclei/mm3 at 7.5 GPa. The fluorescence spectra of obtained diamond crystals contain peaks at 504 nm ( H3-defect), 575 nm (NV-center), and 638 nm (NV-defect), caused by the presence of nitrogen impurity. In the cathodoluminescence spectra, an A-band with the maximum at 470 nm is present. The obtained data make it possible to assign the synthesized diamonds in the carbonate-carbon system to the mixed Ia + Ib type.

The prosthetic implant market is extensive. For example, because of arthritic degeneration of hip and knee cartilage and osteoporotic fractures of the hip, over 200,000 total joint replacements (TJRs) are performed in the United States each year. Current TJR devices are typically metallic (stainless steel, cobalt, or titanium alloy) and are fixed in the bone with polymethylacrylate (PMMA) cement. Carbon-carbon composite materials offer several distinct advantages over metals for TJR prosthesis. Their mechanical properties can be tailored to match more closely the mechanical properties of human bone, and the composite may have up to 25% porosity, the size and distribution of which may be controlled through processing. The porous nature of carbon-carbon composites will allow for the ingrowth of bone, achieving biological fixation, and eliminating the need for PMMA cement fixation.

Of the numerous energy conversion options available for a space nuclear power plant (SNPP), one that shows promise in attaining reliable operation and high efficiency is the direct gas Brayton (GB) system. In order to increase efficiency, the GB system incorporates a recuperator that accounts for nearly half the weight of the energy conversion system (ECS). Therefore, development of a recuperator that is lighter and provides better performance than current heat exchangers could prove to be advantageous. The feasibility of a carbon-carbon (C/C) composite recuperator core has been assessed and a mass savings of 60% and volume penalty of 20% were projected. The excellent thermal properties, high-temperature capabilities, and low density of carbon-carbon materials make them attractive in the GB system, but development issues such as material compatibility with other structural materials in the system, such as refractory metals and superalloys, permeability, corrosion, joining, and fabrication must be addressed.

The failure mechanisms of laminated 2-D carbon/carbon (C/C) and carbon/polyimide (C/P) composites have been determined under inplane biaxial compression loads, and the associated failure envelopes that account for the effect of matrix-type and loading directions, are also obtained. For the C/C laminates, the failure was in the form of micro-kinking of fiber-bundles, interspersed by localized interply delaminations to form the overall shear-fault. The shear fault was aligned with the major use of loading, except at above 75% of balanced biaxial stress, where failure occurred alone both axes. For the C/P laminates, however, the overall failure was primarily in the form of axial interply delaminations aligned with the principal axis of loading, with only secondary events of kinking in few bundles. Although the biaxial strength for both C/C and C/P samples varied significantly with the ratio of in-plane principal stresses, R, there was no variation in the local failure mechanisms. Accordingly, it was found that both materials fail upon achieving a maximum strain along the primary axis of loading.

We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

We present a solid-state NMR methodology capable of investigating the carbon skeleton of natural abundance organic powders. The methodology is based on the (13)C-(13)C dipolar coupling interaction and allows carbon-carbon connectivities to be unambiguously established for a wide range of organic solids. This methodology is particularly suitable for disordered solids, such as natural or synthetic macromolecules, which cannot be studied using conventional diffraction or NMR techniques. PMID:27319808

A.c. calorimetry was used to determine the value of the specific heat at low temperatures for a sample of Textron's fine weave pierced fabric (FWPF) composite, a three-directional carbon-carbon composite with orthogonal fibre orientation. The heat capacity measurements were performed from 30 to 100 K at nearly 1 K intervals. The specific heat values for the composite are similar to those reported in the literature for graphite in the same temperature range.

Thermographic inspection is a viable technique for detecting in-service damage in reinforced carbon-carbon (RCC) composites that are used for thermal protection in the leading edge of the shuttle orbiter. A thermographic technique for detection of near surface flaws in RCC composite structures is presented. A finite element model of the heat diffusion in structures with expected flaw configurations is in good agreement with the experimental measurements.

In this Communication, the living block copolymerization of functionalized cyclohexene oxides and CO{sub 2} is described, yielding multiblock poly(cyclohexene carbonate)s [p(CHC)s] with a diverse range of functionality on the side chains and good control of block sequence and length. Unlike prior systems that contain stable vinyl backbones, the carbonate backbones of polymers reported herein are degradable, allowing possible applications where removable templates are required.

Reinforced carbon-carbon, which is used as thermal protection on the space shuttle orbiter wing leading edges and nose cap, was tested in both radiant and plasma arcjet heating test facilities. The test series was conducted at varying temperatures and pressures. Samples tested in the plasma arcjet facility had consistently higher mass loss than those samples tested in the radiant facility. A method using the mass loss data is suggested for predicting mission mass loss for specific locations on the Orbiter.

Close-up view of the Reinforced Carbon-Carbon nose cap on the front fuselage of the Orbiter Discovery. Note the 76-wheeled orbiter transfer system attached to the orbiter at the forward attach point, the same attach point used to mount the orbiter onto the External Tank. This view was taken at Kennedy Space Center. - Space Transportation System, Orbiter Discovery (OV-103), Lyndon B. Johnson Space Center, 2101 NASA Parkway, Houston, Harris County, TX

This article describes a model for the numerical simulation of liquid silicon infiltration into porous carbon/carbon preforms. Macroscopic silicon concentration has been calculated from capillary flow equations. As a result, time dependence of silicon concentration during infiltration as well as silicon distribution in the ceramic end product can be calculated. Simulation values of silicon concentration after infiltration are in good accordance with experimental measurements.

Carbon-carbon and carbon-polyimide composites are being considered for use as radiator face sheets or fins for space radiator applications. Several traditional white thermal control paints are being considered for the surface of the composite face sheets or fins. One threat to radiator performance is high energy electrons. The durability of the thermal control paints applied to the carbon-carbon and carbon-polyimide composites was evaluated after extended exposure to 4.5 MeV electrons. Electron exposure was conducted under argon utilizing a Mylar(TradeMark) bag enclosure. Solar absorptance and infrared emittance was evaluated before and after exposure to identify optical properties degradation. Adhesion of the paints to the carbon-carbon and carbon-polyimide composite substrates was also of interest. Adhesion was evaluated on pristine and electron beam exposed coupons using a variation of the ASTM D-3359 tape test. Results of the optical properties evaluation and the adhesion tape tests are summarized.

The significant potential of carbon-carbon composites for high-temperature structural applications is well established. For hypersonic vehicle applications, desirable properties include low density, high specific strength and stiffness, low coefficients of thermal expansion, and retention of mechanical properties above 3000 F. A significant problem associated with carbon materials, however, is that they oxidize rapidly in air at temperatures above about 800 F, and therefore must be protected from oxidation. Successful development of effective methods of oxidation protection is key to the eventual utilization of carbon-carbon composites on hypersonic vehicles such as NASP. In this presentation, the basic elements of an oxidation-protection system are described. Results from oxidation-performance evaluations of state-of-the-art ACC-4 type material in simulated airframe vehicle environments (temperature, pressure, and time) conducted at NASA Langley are also presented. NASA Langley has an active research effort to improve the oxidation resistance of carbon-carbon materials for airframe structural and vehicle thermal protection applications. Conversion coating and sealant development research is highlighted.

An advanced carbon-carbon structural component is being experimentally evaluated for use as primary load carrying structure for future single-stage-to-orbit (SSTO) vehicles. The component is a wing torque box section featuring an advanced, three-spar design. This design features 3D-woven, angle-interlock skins, 3D integrally woven spar webs and caps, oxidation inhibited matrix, chemical vapor deposited (CVD) oxidation protection coating, and ceramic matrix composite fasteners. The box spar caps are nested into the skins which, when processed together through the carbon-carbon processing cycle, resulted in monolithic box halves. The box half sections were then joined at the spar web intersections using ceramic matrix composite fasteners. This method of fabrication eliminated fasteners through both the upper and lower skins. Development of the carbon-carbon wing box structure was accomplished in a four phase design and fabrication effort, conducted by Boeing, Information, Space and Defense Systems, Seattle, WA, under contract to the Air Force Research Laboratory (AFRL). The box is now set up for testing and will soon begin cyclic loads testing in the AFRL Structural Test Facility at Wright-Patterson Air Force Base (WPAFB), OH. This paper discusses the latest test setup accomplishments and the results of the pre-cyclic loads testing performed to date.

The present paper is aimed to study the preparation and application of individual artificial bone of carbon/carbon composites. Using computer tomography images (CT), we acquired a three-dimensional image. Firstly, we described bone contour line outlined with manual and automatic method by the binary volume data. Secondly, we created 3D object surface information by marching cubes. Finally, we converted this information to non-uniform rational B-spine (NURBS) by using geomagic software. Individual artificial bone with carbon/carbon composite was prepared through the CNC Machining Center. We replaced the humeral head of the tested rabbit, and then observed the effects of implantation in neuroimaging and pathological section. Using this method, we found that the bone shape processed and bone shape replaced was consistent. After implantation, the implant and the surrounding bone tissue bound closely, and bone tissue grew well on the surface of the implant. It has laid a sound foundation of the preparation using this method for individual artificial bone of carbon/carbon composite material. PMID:24645609

We will discuss latest developments and applications of the USPEX code [1] to carbon-based materials: -We predicted structures of two high-pressure phases of CaCO3 [2] and two complex new high-pressure structures of MgCO3 [3], and our predictions have just been confirmed by experiment. We find that in the top part of the Earth's mantle diamond and MgCO3 magnesite will be the main host of C, but most of the lower mantle will contain carbon in the form of Fe3C cementite, diamond and MgCO3 phases (magnesite and post-magnesite phase). In the D" layer, CaCO3 with a pyroxene-like structure will be stable. -For the Fe-C system at pressures of the Earth's inner core, contrary to conventional wisdom, Fe3C and Fe7C3 are not thermodynamically stable compounds at relevant pressures - the only stable iron carbide is the orthorhombic (Pnma) phase of Fe2C [4]. The upper bound for the carbon content in the inner core is 11-15 mol.% (2.6-3.7 wt.%), and we conclude that carbon is a likely important light alloying element in the core. -We studied possible decomposition of methane. We confirm [5] that methane on compression initially polymerizes into ethane and butane, and it still higher pressures diamond is formed. Thus, it is confirmed that heat can be is produced in Neptune's interior by sinking large amounts of diamond. -Now it is possible to perform optimization of physical properties, e,g, the density and hardness [6,7], which allowed the predicted the densest possible structures of carbon [6]. These are up to 3.2% denser than diamond and possess interesting optical and electronic properties and their strong similarities with known phases of silica, quartz and keatite. It was also proven [7] that diamond is the hardest possible allotrope of carbon. -The evolutionary metadynamics technique [8] allowed us to predict the full set of candidate structures that could be formed upon low-temperature compression of graphite [9]. This includes our earlier proposed [1,10] monoclinic (M

Carbon/carbon (C/C) is an established engineering material used extensively in aerospace. The beneficial properties of C/C include high strength, low density, and toughness. Its shortcoming is its limited usability at temperatures higher than the oxidation temperature of carbon . approximately 400 C. Ceramic matrix composites (CMCs) are used instead, but carry a weight penalty. Combining a thin laminate of CMC to a bulk structure of C/C retains all of the benefits of C/C with the high temperature oxidizing environment usability of CMCs. Ultramet demonstrated the feasibility of combining the light weight of C/C composites with the oxidation resistance of zirconium carbide (ZrC) and zirconium- silicon carbide (Zr-Si-C) CMCs in a unique system composed of a C/C primary structure with an integral CMC liner with temperature capability up to 4,200 F (.2,315 C). The system effectively bridged the gap in weight and performance between coated C/C and bulk CMCs. Fabrication was demonstrated through an innovative variant of Ultramet fs rapid, pressureless melt infiltration processing technology. The fully developed material system has strength that is comparable with that of C/C, lower density than Cf/SiC, and ultra-high-temperature oxidation stability. Application of the reinforced ceramic casing to a predominantly C/C structure creates a highly innovative material with the potential to achieve the long-sought goal of long-term, cyclic high-temperature use of C/C in an oxidizing environment. The C/C substructure provided most of the mechanical integrity, and the CMC strengths achieved appeared to be sufficient to allow the CMC to perform its primary function of protecting the C/C. Nozzle extension components were fabricated and successfully hot-fire tested. Test results showed good thermochemical and thermomechanical stability of the CMC, as well as excellent interfacial bonding between the CMC liner and the underlying C/C structure. In particular, hafnium-containing CMCs on

Carbon-carbon (C/C) composites are notable among engineering materials in aerospace and defense industries possessing excellent specific mechanical, thermal, frictional and wear properties. C/C maintain their properties at temperatures where most of the high end alloys give in, and maintain their dimensional stability at temperatures above 2000 °C. C/C is frequently used in aircraft and automotive industries as brake materials. However, frictional performance is dependent on various parameters: microstructure, fiber type, fiber orientation distribution, fiber/matrix interfacial bond, heat treatment, and oxidation. The present study in dissertation provides an insight into the impact of heat treatment, and oxidation on microstructure, mechanical and thermal properties. The heat treatment (performed at 1800, 2100, 2400 °C in argon) of two-directional (2-D) pitch-fiber with charred resin carbon matrix, and three-directional (3-D) PAN-fiber with CVI carbon matrix influenced microstructure, mechanical and thermal properties. Microstructure characterized by polarized light microscopy (PLM), XRD, and Raman spectroscopy changed with increasing heat treatment temperature. The RL microstructure of 3-D C/C progressively highly organized, whereas ISO microstructure of 2-D C/C's charred resin hardly organized into an ordered structure as evident from Raman spectroscopy and Raman profiling of polished samples. Pitch-fiber organized more than the ISO microstructure of charred resin matrix. On the other, PAN-fiber became more ordered, but was organization was lower than pitch-fiber. Thermal conductivity increased for both (2-D, 3-D C/C) materials in comparison to non-heat treated (NHT) C/Cs. Thermal conductivity of oxidized samples decreased significantly than non-oxidized samples. In-plane thermal conductivity of 3-D C/C was much higher than that of 2-D C/C, and was attributed to the rough laminar (RL) microstructure of carbon matrix and continuous PAN-fiber when compared to

The hedgehog molecule: A simple ethynyl dithiocarbamate [Ar-C≡C-S-C(S)NR(2)] is able to cleave a broad range of enthalpically strong σ bonds and to activate carbon dioxide and elemental sulfur. Depending on the substrate, the bond activation process involves either the existence of an equilibrium with the nonobservable mesoionic carbene isomer or the cooperation of the nucleophilic carbon-carbon triple bond and the electrophilic CS carbon atom. PMID:23210141

Multi-walled carbon nanotube (MWCNT)-based carbon/carbon composites were fabricated by the chemical vapor infiltration of pyrolytic carbon into pre-compressed MWCNT blocks. The pyrolytic carbon was deposited on the surface of the MWCNTs and filled the gaps between the MWCNTs, which improved the connection between the MWCNTs and formed a three-dimensional network structure. The mechanical and electrical properties were improved significantly. The values of the maximum compressed deformation, maximum breaking strength, Young's modulus and energy absorption are measured as 10.9%, 148.6 MPa, 1588.6 MPa and 13.8 kJ kg-1, respectively. The conductivity reached about 204.4 S cm-1, more than 10 times larger than that of pre-compressed MWCNT blocks. After annealing at 1800 °C in vacuum, the graphitization improved remarkably. The pyrolytic carbon deposited on the surface of the MWCNTs was rearranged along the walls, and resulted in an increase of the number of walls of the MWCNTs.Multi-walled carbon nanotube (MWCNT)-based carbon/carbon composites were fabricated by the chemical vapor infiltration of pyrolytic carbon into pre-compressed MWCNT blocks. The pyrolytic carbon was deposited on the surface of the MWCNTs and filled the gaps between the MWCNTs, which improved the connection between the MWCNTs and formed a three-dimensional network structure. The mechanical and electrical properties were improved significantly. The values of the maximum compressed deformation, maximum breaking strength, Young's modulus and energy absorption are measured as 10.9%, 148.6 MPa, 1588.6 MPa and 13.8 kJ kg-1, respectively. The conductivity reached about 204.4 S cm-1, more than 10 times larger than that of pre-compressed MWCNT blocks. After annealing at 1800 °C in vacuum, the graphitization improved remarkably. The pyrolytic carbon deposited on the surface of the MWCNTs was rearranged along the walls, and resulted in an increase of the number of walls of the MWCNTs. Electronic supplementary

This report describes a combined experimental and computational investigation of the mechanism of C(sp(3))-N bond-forming reductive elimination from sulfonamide-ligated Pd(IV) complexes. After an initial experimental assessment of reactivity, we used ZStruct, a computational combinatorial reaction finding method, to analyze a large number of multistep mechanisms for this process. This study reveals two facile isomerization pathways connecting the experimentally observed Pd(IV) isomers, along with two competing SN2 pathways for C(sp(3))-N coupling. One of these pathways involves an unanticipated oxygen-nitrogen exchange of the sulfonamide ligand prior to an inner-sphere SN2-type reductive elimination. The calculated ΔG(⧧) values for isomerization and reductive elimination with a series of sulfonamide derivatives are in good agreement with experimental data. Furthermore, the simulations predict relative reaction rates with different sulfonamides, which is successful only after considering competition between the proposed operating mechanisms. Overall, this work shows that the combination of experimental studies and new computational tools can provide fundamental mechanistic insights into complex organometallic reaction pathways. PMID:27087364

Isobenzofuran-1(3H)-ones (phtalides) are heterocycles that present a benzene ring fused to a γ-lactone functionality. This structural motif is found in several natural and synthetic compounds that present relevant biological activities. In the present investigation, the 3-(2-hydroxy-4,4-dimethyl-6-oxocyclohexen-1-yl)isobenzofuran-1(3H)-one was characterized by single-crystal X-ray analysis. In the crystal structure, there are two molecules per asymmetric unit. One of them exhibits resonance assisted hydrogen bonds (RAHBs). Semi-empirical and DFT calculations were performed to obtain electronic structure and π-delocalization parameters, in order to better understand the energy stabilization of RAHBs in the crystal packing of the studied molecule. The structural parameters showed good agreement between theoretical and experimental data. The theoretical investigation revealed that the RAHBs stabilization energy is directly related to the electronic delocalization of the enol form fragment. In addition, RAHBs significantly affected the HOMO and charge distribution around the conjugated system. PMID:27410224

Channel geometry governs the unitary osmotic water channel permeability, pf, according to classical hydrodynamics. Yet, pf varies by several orders of magnitude for membrane channels with a constriction zone that is one water molecule in width and four to eight molecules in length. We show that both the pf of those channels and the diffusion coefficient of the single-file waters within them are determined by the number NH of residues in the channel wall that may form a hydrogen bond with the single-file waters. The logarithmic dependence of water diffusivity on NH is in line with the multiplicity of binding options at higher NH densities. We obtained high-precision pf values by (i) having measured the abundance of the reconstituted aquaporins in the vesicular membrane via fluorescence correlation spectroscopy and via high-speed atomic force microscopy, and (ii) having acquired the vesicular water efflux from scattered light intensities via our new adaptation of the Rayleigh-Gans-Debye equation. PMID:26167541

Analysis of the pH dependence of the kinetic parameters and competitive inhibitor Ki values for tryptophan indole-lyase suggests two enzymic groups must be unprotonated in order to facilitate binding and catalysis of tryptophan. The V/K for tryptophan and the pKi for oxindolyl-L-alanine, a putative transition state analogue and competitive inhibitor, decrease below two pK values of 7.6 and 6.0, while the Ki for L-alanine, also a competitive inhibitor, is 3300-fold larger (20 mM) than that for oxindolyl-L-alanine and increases below a single pK of 7.6. A single pK of 7.6 is also observed in the V/K profile for the alternate substrate, S-methyl-L-cysteine. Therefore, the enzymic group with a pK of 7.6 is responsible for proton abstraction at the 2-position of tryptophan, while the enzymic group with a pK of 6.0 interacts with the indole portion of tryptophan and probably catalyzes formation of the indolenine tautomer of tryptophan (in concert with proton transfer to C-3 of indole from the group with pK 7.6) to facilitate carbon-carbonbond cleavage and elimination of indole. The pH variation of the primary deuterium isotope effects for proton abstraction at the 2-position of tryptophan (DV = 2.5 and D(V/Ktrp) = 2.8) are pH independent, while the Vmax for tryptophan or S-methyl-L-cysteine is the same and also pH independent. Thus, substrates bind only to the correctly protonated form of the enzyme. Further, tryptophan is not sticky, and the pK values observed in both V/K profiles are the correct ones.

X-ray crystal structures of the metcyano form of dehaloperoxidase-hemoglobin (DHP A) from Amphitrite ornata (DHPCN) and the C73S mutant of DHP A (C73SCN) were determined using synchrotron radiation in order to further investigate the geometry of diatomic ligands coordinated to the heme iron. The DHPCN structure was also determined using a rotating-anode source. The structures show evidence of photoreduction of the iron accompanied by dissociation of bound cyanide ion (CN{sup -}) that depend on the intensity of the X-ray radiation and the exposure time. The electron density is consistent with diatomic molecules located in two sites in the distal pocket of DHPCN. However, the identities of the diatomic ligands at these two sites are not uniquely determined by the electron-density map. Consequently, density functional theory calculations were conducted in order to determine whether the bond lengths, angles and dissociation energies are consistent with bound CN{sup -} or O{sub 2} in the iron-bound site. In addition, molecular-dynamics simulations were carried out in order to determine whether the dynamics are consistent with trapped CN{sup -} or O{sub 2} in the second site of the distal pocket. Based on these calculations and comparison with a previously determined X-ray crystal structure of the C73S-O{sub 2} form of DHP [de Serrano et al. (2007), Acta Cryst. D63, 1094-1101], it is concluded that CN{sup -} is gradually replaced by O{sub 2} as crystalline DHP is photoreduced at 100 K. The ease of photoreduction of DHP A is consistent with the reduction potential, but suggests an alternative activation mechanism for DHP A compared with other peroxidases, which typically have reduction potentials that are 0.5 V more negative. The lability of CN{sup -} at 100 K suggests that the distal pocket of DHP A has greater flexibility than most other hemoglobins.

The strength of brittle materials is characterized by a wide scatter. Such materials are also afflicted by size effects. Size effects in brittle composite structures such as beams and plates with and without stress raisers are investigated experimentally and analytically. A methodology for reliability analysis of carbon-carbon composites is presented. The model is based on Weibull statistics which was extended to account for the three-dimensional stress field including interlaminar stresses. Failure criteria for bi-directional orthotropic lamina are developed and failure analysis in the non-probabilistic sense (i.e., first-ply-failure analysis) is performed. Comparisons are made with existing failure criteria, with the results of the reliability analysis and also with experiments.

The results of laboratory testing and modeling activities conducted to support the development of waste forms to immobilize wastes generated during the electrometallurgical treatment of spent sodium-bonded nuclear fuel and their qualification for disposal in the federal high-level radioactive waste repository are summarized in this report. Tests and analyses were conducted to address issues related to the chemical, physical, and radiological properties of the waste forms relevant to qualification. These include the effects of composition and thermal treatments on the phase stability, radiation effects, and methods for monitoring product consistency. Other tests were conducted to characterize the degradation and radionuclide release behaviors of the ceramic waste form (CWF) used to immobilize waste salt and the metallic waste form (MWF) used to immobilize metallic wastes and to develop models for calculating the release of radionuclides over long times under repository-relevant conditions. Most radionuclides are contained in the binder glass phase of the CWF and in the intermetallic phase of the MWF. The release of radionuclides from the CWF is controlled by the dissolution rate of the binder glass, which can be tracked using the same degradation model that is used for high-level radioactive waste (HLW) glass. Model parameters measured for the aqueous dissolution of the binder glass are used to model the release of radionuclides from a CWF under all water-contact conditions. The release of radionuclides from the MWF is element-specific, but the release of U occurs the fastest under most test conditions. The fastest released constituent was used to represent all radionuclides in model development. An empirical aqueous degradation model was developed to describe the dependence of the radionuclide release rate from a MWF on time, pH, temperature, and the Cl{sup -} concentration. The models for radionuclide release from the CWF and MWF are both bounded by the HLW glass

... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

... REPAIRS UNDER NATIONAL SHIPPING AUTHORITY MASTER LUMP SUM REPAIR CONTRACT-NSA-LUMPSUMREP Sec. 10 Bonds. (a... awarded work and the furnishing of the performance and payment bonds required by Article 14 of the NSA... of the NSA-LUMPSUMREP Contract, the standard form of individual performance bond (Standard Form...

Another spinoff to the food processing industry involves a dry lubricant developed by General Magnaplate Corp. of Linden, N.J. Used in such spacecraft as Apollo, Skylab and Viking, the lubricant is a coating bonded to metal surfaces providing permanent lubrication and corrosion resistance. The coating lengthens equipment life and permits machinery to be operated at greater speed, thus increasing productivity and reducing costs. Bonded lubricants are used in scores of commercia1 applications. They have proved particularly valuable to food processing firms because, while increasing production efficiency, they also help meet the stringent USDA sanitation codes for food-handling equipment. For example, a cookie manufacturer plagued production interruptions because sticky batter was clogging the cookie molds had the brass molds coated to solve the problem. Similarly, a pasta producer faced USDA action on a sanitation violation because dough was clinging to an automatic ravioli-forming machine; use of the anti-stick coating on the steel forming plates solved the dual problem of sanitation deficiency and production line downtime.

A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

The Columbia accident has focused attention on the critical need for on-orbit repair concepts for wing leading edges in the event that potentially catastrophic damage is incurred during Space Shuttle Orbiter flight. The leading edge of the space shuttle wings consists of a series of eleven panels on each side of the orbiter. These panels are fabricated from reinforced carbon-carbon (RCC) which is a light weight composite with attractive strength at very high temperatures. The damage that was responsible for the loss of the Colombia space shuttle was deemed due to formation of a large hole in one these RCC leading edge panels produced by the impact of a large piece of foam. However, even small cracks in the RCC are considered as potentially catastrophic because of the high temperature re-entry environment. After the Columbia accident, NASA has explored various means to perform on-orbit repairs in the event that damage is sustained in future shuttle flights. Although large areas of damage, such as that which doomed Columbia, are not anticipated to re-occur due to various improvements to the shuttle, especially the foam attachment, NASA has also explored various options for both small and large area repair. This paper reports one large area repair concept referred to as the "metallic over-wrap." Environmental conditions during re-entry of the orbiter impose extreme requirements on the RCC leading edges as well as on any repair concepts. These requirements include temperatures up to 3000 F (1650 C) for up to 15 minutes in the presence of an extremely oxidizing plasma environment. Figure 1 shows the temperature profile across one panel (#9) which is subject to the highest temperatures during re-entry. Although the RCC possesses adequate mechanical strength at these temperatures, it lacks oxidation resistance. Oxidation protection is afforded by converting the outer layers of the RCC to SiC by chemical vapor deposition (CVD). At high temperatures in an oxidizing

The IR spectrum of catechol in CCl(4) shows two fairly sharp O-H stretching bands of roughly equal absorbance at 3615.0 and 3569.6 cm(-1) due, respectively, to the "free" OH and the intramolecularly H-bonded OH groups. Intermolecular H-bond formation between the "free" OH and a hydrogen bond acceptor (HBA) decreases its stretching frequency by several hundred wavenumbers and simultaneously decreases the frequency of the intramolecularly H-bonded OH by a few tens of wavenumbers. The magnitude of these frequency shifts, Deltaupsilon(inter) and Deltaupsilon(intra), respectively, are very well reproduced by DFT calculations. As would be expected, the magnitudes of Deltaupsilon(inter) and Deltaupsilon(intra) increase as the HB accepting ability of the HBA increases as quantified, on a relative scale, by the HBA's values (Abraham et al. J. Chem. Soc. Perkin Trans. 2 1990, 521). However, plots of experimental, or calculated, frequency shifts versus reveal that Deltaupsilon(inter) and Deltaupsilon(intra) are ca. 40% larger for a nitrogen atom HBA than for an oxygen atom HBA having equal HBA activity. We hypothesize that for HBAs of equal strength, i.e., of equal, the H-bond in (O-H- - -O)(inter) is shorter and, hence, intrinsically stronger than the H-bond in the (O-H- - -N)(inter). However, we further hypothesize that there is more charge separation in the H-bond to N because N is a better proton acceptor than O. Hence, it is the greater Coulombic attraction in (O-H- - -N)(inter) which strengthens this H-bond and compensates for its greater length. Theoretical calculations lend support to these hypotheses. PMID:14624616

Reusable, oxidation-protected reinforced carbon-carbon (RCC) has been successfully flown on all Shuttle Orbiter flights. Thermal testing of the silicon carbide-coated RCC to determine its oxidation characteristics has been performed in convective (plasma Arc-Jet) heating facilities. Surface sealant mass loss was characterized as a function of temperature and pressure. High-temperature testing was performed to develop coating recession correlations for predicting performance at the over-temperature flight conditions associated with abort trajectories. Methods for using these test data to establish multi-mission re-use (i.e., mission life) and single mission limits are presented.

A micromechanical methodology has been developed for analyzing fiber bridging and resistance-curve behavior in reinforced-carbon-carbon (RCC) panels with a three-dimensional (3D) composite architecture and a silicon carbide (SiC) surface coating. The methodology involves treating fiber bridging traction on the crack surfaces in terms of a weight function approach and a bridging law that relates the bridging stress to the crack opening displacement. A procedure has been developed to deduce material constants in the bridging law from the linear portion of the K-resistance curve. This report contains information on the application of procedures and outcomes.

Ge/Si and other nonsilicon film heterostructures are formed by hydrogen-induced exfoliation of the Ge film which is wafer bonded to a cheaper substrate, such as Si. A thin, single-crystal layer of Ge is transferred to Si substrate. The bond at the interface of the Ge/Si heterostructures is covalent to ensure good thermal contact, mechanical strength, and to enable the formation of an ohmic contact between the Si substrate and Ge layers. To accomplish this type of bond, hydrophobic wafer bonding is used, because as the invention demonstrates the hydrogen-surface-terminating species that facilitate van der Waals bonding evolves at temperatures above 600.degree. C. into covalent bonding in hydrophobically bound Ge/Si layer transferred systems.

Parkinson's disease has long been known to involve the loss of dopaminergic neurons in the substantia nigra and the coincidental appearance of Lewy bodies containing oligomerized forms of α-synuclein. The "catecholaldehyde hypothesis" posits a causal link between these two central pathologies mediated by 3,4-dihydroxyphenylacetaldehyde (DOPAL), the most toxic dopamine metabolite. Here we determine the structure of the dominant product in reactions between DOPAL and α-synuclein, a dicatechol pyrrole lysine adduct. This novel modification results from the addition of two DOPAL molecules to the Lys sidechain amine through their aldehyde moieties and the formation of a new carbon-carbonbond between their alkyl chains to generate a pyrrole ring. The product is detectable at low concentrations of DOPAL and its discovery should provide a valuable chemical basis for future studies of DOPAL-induced crosslinking of α-synuclein. PMID:27158766

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

The photocatalytic H2-production from water by using different aliphatic alcohols as sacrifice agent, over Pt/TiO2 nanotube, has been studied. The rate of H2-production over Pt/TiO2 showed the following trend: methanol > ethanol > i-propanol > n-propanol > sec-butanol > tert-butanol. Moreover, it was found that the aliphatic alcohols after photocatalytic reaction, including ethanol, n-propanol, i-propanol, sec-butanol and tert-butanol, were successfully coupled to corresponding dihydric alcohol such as 2,3-butanol, pinacol, 3,4-hexanediol, 3,4-dimethyl-3,4-hexanediol and 2,5-dimethyl-2,5-hexanediol. The effect of reaction condition on the Csbnd C coupling of alcohols was also investigated, and the possible mechanism of Csbnd C coupling depend on whether α-C radicals oxidized by hole or rad OH can fast strip from the TiO2 surface.

... a public charge. A bond may also be cancelled in order to allow substitution of another bond. A... surety bonds posted in immigration cases shall be executed on Form I-352, Immigration Bond, a copy of... to approve a bond, a formal agreement to extension of liability of surety, a request for delivery...

... a public charge. A bond may also be cancelled in order to allow substitution of another bond. A... surety bonds posted in immigration cases shall be executed on Form I-352, Immigration Bond, a copy of... to approve a bond, a formal agreement to extension of liability of surety, a request for delivery...

... a public charge. A bond may also be cancelled in order to allow substitution of another bond. A... surety bonds posted in immigration cases shall be executed on Form I-352, Immigration Bond, a copy of... to approve a bond, a formal agreement to extension of liability of surety, a request for delivery...

Conspectus The ynamide functional group activates carbon-carbon triple bonds through an attached nitrogen atom that bears an electron-withdrawing group. As a result, the alkyne has both electrophilic and nucleophilic properties. Through the selection of the electron-withdrawing group attached to nitrogen chemists can modulate the electronic properties and reactivity of ynamides, making these groups versatile synthetic building blocks. The reactions of ynamides also lead directly to nitrogen-containing products, which provides access to important structural motifs found in natural products and molecules of medicinal interest. Therefore, researchers have invested increasing time and research in the chemistry of ynamides in recent years. This Account surveys and assesses new organic transformations involving ynamides developed in our laboratory and in others around the world. We showcase the synthetic power of ynamides for rapid assembly of complex molecular structures. Among the recent reports of ynamide transformations, ring-forming reactions provide a powerful tool for generating molecular complexity quickly. In addition to their synthetic utility, such reactions are mechanistically interesting. Therefore, we focus primarily on the cyclization chemistry of ynamides. This Account highlights ynamide reactions that are useful in the rapid synthesis of cyclic and polycyclic structural manifolds. We discuss the mechanisms active in the ring formations and describe representative examples that demonstrate the scope of these reactions and provide mechanistic insights. In this discussion we feature examples of ynamide reactions involving radical cyclizations, ring-closing metathesis, transition metal and non-transition metal mediated cyclizations, cycloaddition reactions, and rearrangements. The transformations presented rapidly introduce structural complexity and include nitrogen within, or in close proximity to, a newly formed ring (or rings). Thus, ynamides have emerged

In the title salt, C14H18N2(2+) · 2C9H5N4O(-), the 1,1'-diethyl-4,4'-bipyridine-1,1'-diium dication lies across a centre of inversion in the space group P21/c. In the 1,1,3,3-tetracyano-2-ethoxypropenide anion, the two independent -C(CN)2 units are rotated, in conrotatory fashion, out of the plane of the central propenide unit, making dihedral angles with the central unit of 16.0(2) and 23.0(2)°. The ionic components are linked by C-H...N hydrogen bonds to form a complex sheet structure, within which each cation acts as a sixfold donor of hydrogen bonds and each anion acts as a threefold acceptor of hydrogen bonds. PMID:24594730

The performance and safety of the radioisotope power source depend in part on the thermal and impact properties of the materials used in the general purpose heat source (GPHS) through the use of an impact shell, thermal insulation and an aeroshell. Within the aeroshell are two graphite impact shells, made of fine-weave pierced-fabric (FWPF) that encapsulate four iridium alloy clad isotopic fuel pellets and provides impact protection for the clad. Impact studies conducted at Los Alamos National Laboratory showed that impact shells typically fractured parallel to their longitudinal axis. The objective of this effort is to develop new impact shell concepts with improved performance. An effort to develop alternative carbon-carbon composites for the graphite impact shell was conducted. Eight braided architectures were examined in this study. The effects of the number of graphitization cycles on both the density and circumferential strength of these braided structures were determined. Results show that a filament wound carbon-carbon composite possesses the desired density and circumferential strength important to GPHS. .

The characterization of soil attributes using hyperspectral sensors has revealed patterns in soil spectra that are known to respond to mineral composition, organic matter, soil moisture and particle size distribution. Soil samples from different soil horizons of replicated soil series from sites located within Washington and Oregon were analyzed with the FieldSpec Spectroradiometer to measure their spectral signatures across the electromagnetic range of 400 to 1,000 nm. Similarity rankings of individual soil samples reveal differences between replicate series as well as samples within the same replicate series. Using classification and regression tree statistical methods, regression trees were fitted to each spectral response using concentrations of nitrogen, carbon, carbonate and organic matter as the response variables. Statistics resulting from fitted trees were: nitrogen R2 0.91 (p < 0.01) at 403, 470, 687, and 846 nm spectral band widths, carbonate R2 0.95 (p < 0.01) at 531 and 898 nm band widths, total carbon R2 0.93 (p < 0.01) at 400, 409, 441 and 907 nm band widths, and organic matter R2 0.98 (p < 0.01) at 300, 400, 441, 832 and 907 nm band widths. Use of the 400 to 1,000 nm electromagnetic range utilizing regression trees provided a powerful, rapid and inexpensive method for assessing nitrogen, carbon, carbonate and organic matter for upper soil horizons in a nondestructive method. PMID:23112620

A nanostructured polypyrrole powder was synthesized in a previous work from the oxidation of pyrrole by a nanostructured MnO2 powder used simultaneously as an oxidizing agent and a sacrificial template in a redox heterogeneous mechanism. In this study, this original PPy powder was used as an active additive material with different ratio in carbon/carbon symmetrical supercapacitors whose performances were studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) using a Swagelok-type cell. From the EIS spectra, the complex capacitance was extracted using a model involving two Cole-Cole type complex capacitances linked in series. The specific capacitance values evaluated by EIS and cyclic voltammetry are in a good agreement between them. The results show that the addition of nanostructured polypyrrole powder improves significantly the specific capacitance of the carbon electrode and consequently the performances of carbon/carbon supercapacitors. The original and versatile synthesis method used to produce this polypyrrole powder appears to be attractive for large scale production of promising additives for electrode materials of supercapacitors.

In this study, coated reinforced carbon-carbon (RCC) samples of similar structure and composition as that from the NASA space shuttle orbiter's thermal protection system were fabricated with slots in their coating simulating craze cracks. These specimens were used to study oxidation damage detection and characterization using nondestructive evaluation (NDE) methods. These specimens were heat treated in air at 1143 C and 1200 C to create cavities in the carbon substrate underneath the coating as oxygen reacted with the carbon and resulted in its consumption. The cavities varied in diameter from approximately 1 to 3mm. Single-sided NDE methods were used because they might be practical for on-wing inspection, while X-ray micro-computed tomography (CT) was used to measure cavity sizes in order to validate oxidation models under development for carbon-carbon materials. An RCC sample having a naturally cracked coating and subsequent oxidation damage was also studied with X-ray micro-CT. This effort is a follow-on study to one that characterized NDE methods for assessing oxidation damage in an RCC sample with drilled holes in the coating.

In this study, coated reinforced carbon-carbon (RCC) samples of similar structure and composition as that from the NASA space shuttle orbiter's thermal protection system were fabricated with slots in their coating simulating craze cracks. These specimens were used to study oxidation damage detection and characterization using nondestructive evaluation (NDE) methods. These specimens were heat treated in air at 1143 and 1200 C to create cavities in the carbon substrate underneath the coating as oxygen reacted with the carbon and resulted in its consumption. The cavities varied in diameter from approximately 1 to 3 mm. Single-sided NDE methods were used since they might be practical for on-wing inspection, while x-ray micro-computed tomography (CT) was used to measure cavity sizes in order to validate oxidation models under development for carbon-carbon materials. An RCC sample having a naturally-cracked coating and subsequent oxidation damage was also studied with x-ray micro-CT. This effort is a follow-on study to one that characterized NDE methods for assessing oxidation damage in an RCC sample with drilled holes in the coating.

The characterization of soil attributes using hyperspectral sensors has revealed patterns in soil spectra that are known to respond to mineral composition, organic matter, soil moisture and particle size distribution. Soil samples from different soil horizons of replicated soil series from sites located within Washington and Oregon were analyzed with the FieldSpec Spectroradiometer to measure their spectral signatures across the electromagnetic range of 400 to 1,000 nm. Similarity rankings of individual soil samples reveal differences between replicate series as well as samples within the same replicate series. Using classification and regression tree statistical methods, regression trees were fitted to each spectral response using concentrations of nitrogen, carbon, carbonate and organic matter as the response variables. Statistics resulting from fitted trees were: nitrogen R(2) 0.91 (p < 0.01) at 403, 470, 687, and 846 nm spectral band widths, carbonate R(2) 0.95 (p < 0.01) at 531 and 898 nm band widths, total carbon R(2) 0.93 (p < 0.01) at 400, 409, 441 and 907 nm band widths, and organic matter R(2) 0.98 (p < 0.01) at 300, 400, 441, 832 and 907 nm band widths. Use of the 400 to 1,000 nm electromagnetic range utilizing regression trees provided a powerful, rapid and inexpensive method for assessing nitrogen, carbon, carbonate and organic matter for upper soil horizons in a nondestructive method. PMID:23112620

The development and application of advanced nondestructive evaluation techniques for the Reinforced Carbon-Carbon (RCC) components of the Space Shuttle Orbiter Leading Edge Structural Subsystem (LESS) was identified as a crucial step toward returning the shuttle fleet to service. In order to help meet this requirement, eddy current techniques have been developed for application to RCC components. Eddy current technology has been found to be particularly useful for measuring the protective coating thickness over the reinforced carbon-carbon and for the identification of near surface cracking and voids in the RCC matrix. Testing has been performed on as manufactured and flown RCC components with both actual and fabricated defects representing impact and oxidation damage. Encouraging initial results have led to the development of two separate eddy current systems for in-situ RCC inspections in the orbiter processing facility. Each of these systems has undergone blind validation testing on a full scale leading edge panel, and recently transitioned to Kennedy Space Center to be applied as a part of a comprehensive RCC inspection strategy to be performed in the orbiter processing facility after each shuttle flight.

Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

... 43 Public Lands: Interior 2 2011-10-01 2011-10-01 false Bonding requirements. 3474.1 Section 3474....1 Bonding requirements. (a) Before a lease may be issued, one of the following forms of lease bond... a form approved by the Director. (c) The bonding obligation for a new lease may be met by...

Compares the coulumbic point charge model for hydrogen chloride with the valence bond model. It is not possible to assign either a nonpolar or ionic canonical form of the valence bond model, while the covalent-ionic bond distribution does conform to the point charge model. (JM)

In the title molecular salt, C12H10N5O+·NO3 −, the adenine unit has an N 9-protonated N(7)—H tautomeric form with non-protonated N1 and N3 atoms. The dihedral angle between the adenine ring system and the phenyl ring is 51.10 (10)°. The typical intra­molecular N7—H⋯O hydrogen bond with an S(7) graph-set motif is also present. The benzoyl­adeninium cations also form base pairs through N—H⋯O and C—H⋯N hydrogen bonds involving the Watson–Crick face of the adenine ring and the C and O atoms of the benzoyl ring of an adjacent cation, forming a supra­molecular ribbon with R 2 2(9) rings. Benzoyl­adeninum cations are also bridged by one of the oxygen atoms of the nitrate anion, which acts as a double acceptor, forming a pair of N—H⋯O hydrogen bonds to generate a second ribbon motif. These ribbons together with π–π stacking inter­actions between the phenyl ring and the five- and six-membered adenine rings of adjacent mol­ecules generate a three-dimensional supra­molecular architecture. PMID:26958373

The Ti-metal/C-C composite joints were formed by reactive brazing with three commercial brazes, namely, Cu-ABA, TiCuNi, and TiCuSiI. The joint microstructures were examined using optical microscopy and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS). The results of the microstructure analysis indicate solute redistribution across the joint and possible metallurgical bond formation via interdiffusion, which led to good wetting and spreading. A tube-on-plate tensile test was used to evaluate joint strength of Ti-tube/ C-C composite joints. The load-carrying ability was greatest for the Cu-ABA braze joint structures. This system appeared to have the best braze spreading which resulted in a larger braze/C-C composite bonded area compared to the other two braze materials. Also, joint loadcarrying ability was found to be higher for joint structures where the fiber tows in the outer ply of the C-C composite were aligned perpendicular to the tube axis when compared to the case where fiber tows were aligned parallel to the tube axis.

Technologies for Space Reactor Power Systems are being developed to enable future NASA's missions early next decade to explore the farthest planets in the solar system. The choices of the energy conversion technology for these power systems require radiator temperatures that span a wide range, from 350 K to 800 K. Heat pipes with carbon-carbon fins and armor are the preferred choice for these radiators because of inherent redundancy and efficient spreading and rejection of waste heat into space at a relatively small mass penalty. The performance results and specific masses of radiator heat pipes with cesium, rubidium, and potassium working fluids are presented and compared in this paper. The heat pipes operate at 40% of the prevailing operation limit (a design margin of 60%), typically the sonic and/or capillary limit. The thickness of the carbon-carbon fins is 0.5 mm but the width is varied, and the evaporator and condenser sections are 0.15 and 1.35 m long, respectively. The 400-mesh wick and the heat pipe thin metal wall are titanium, and the carbon-carbon armor ({approx} 2 mm-thick) provides both structural strength and protection against meteoroids impacts. The cross-section area of the D-shaped radiator heat pipes is optimized for minimum mass. Because of the low vapor pressure of potassium and its very high Figure-Of-Merit (FOM), radiator potassium heat pipes are the best performers at temperatures above 800 K, where the sonic limit is no longer an issue. On the other hand, rubidium heat pipes are limited by the sonic limit below 762 K and by the capillary limit at higher temperature. The transition temperature between these two limits for the cesium heat pipes occurs at a lower temperature of 724 K, since cesium has lower FOM than rubidium. The present results show that with a design margin of 60%, the cesium heat pipes radiator is best at 680-720 K, the rubidium heat pipes radiator is best at 720-800 K, while the potassium heat pipes radiator is the best

The flexural response of SiC-coated carbon-carbon composites (ACC-4) at room and elevated temperatures is presented. Three-point bending tests were performed on virgin and mission-cycled specimens, and the variation in flexural strength is examined. The load-deflection behavior of the material at various temperatures is investigated, and the Weibull (1939) analysis of the strength data is performed. Micrographs of various cross sections in the damaged zone were taken, and the failure mechanisms are discussed. Fatigue tests were conducted under flexural loads, and the S-N diagram with the corresponding Weibull analysis are presented. Untested as well as fractured specimens under static and dynamic loading were C-scanned to identify the damaged zone and visualize the extent of the damage. Failure analyses are presented for both static and cyclic loading on the basis of NDE, the micrographs, and the experimental data.

Based on prior successful fabrication and demonstration testing of a carbon-carbon heat pipe radiator element with integral fins this paper examines the hypothetical extension of the technology via substitution of high thermal conductivity composites which would permit increasing fin length while still maintaining high fin effectiveness. As a result the specific radiator mass could approach an ultimate asymptotic minimum value near 1.0 kg/m2, which is less than one fourth the value of present day satellite radiators. The implied mass savings would be even greater for high capacity space and planetary surface power systems, which may require radiator areas ranging from hundreds to thousands of square meters, depending on system power level.

Flexure, compressive, and shear properties of the carbon matrix in carbon/carbon (C/C) composites made via a pitch impregnation method have been determined. The pitch carbon matrix was made using the same densification cycle used in making the C/C composite. Cyclic compression tests were performed on the matrix specimens. While unloading, a reduction in modulus was observed and residual strains were observed on complete unloading. These features were attributed to the presence of damage and plasticity in the densified matrix. A J 2 plasticity model with damage was used to simulate this behavior numerically. The parameters required for plasticity and damage model were evaluated iteratively by comparing the results in experiments with simulation.

The use of carbon-carbon (C-C) recuperators in closed-Brayton-cycle space power conversion systems was assessed. Recuperator performance was forecast based on notional thermodynamic cycle state values for planetary missions. Resulting thermal performance, mass and volume for plate-fin C-C recuperators were estimated and quantitatively compared with values for conventional offset-strip-fin metallic designs. Mass savings of 40-55% were projected for C-C recuperators with effectiveness greater than 0.9 and thermal loads from 25-1400 kWt. The smaller thermal loads corresponded with lower mass savings; however, at least 50% savings were forecast for all loads above 300 kWt. System-related material challenges and compatibility issues were also discussed.

The feasibility of using carbon-carbon (C-C) recuperators in conceptual closed-Brayton-cycle space power conversion systems was assessed. Recuperator performance expectations were forecast based on notional thermodynamic cycle state values for potential planetary missions. Resulting thermal performance, mass and volume for plate-fin C-C recuperators were estimated and quantitatively compared with values for conventional offset-strip-fin metallic designs. Mass savings of 30 to 60 percent were projected for C-C recuperators with effectiveness greater than 0.9 and thermal loads from 25 to 1400 kWt. The smaller thermal loads corresponded with lower mass savings; however, 60 percent savings were forecast for all loads above 300 kWt. System-related material challenges and compatibility issues were also discussed.

It is noted that the Shuttle Orbiter will be more subject to meteoroid impact than previous spacecraft, due to its greater surface area and longer cumulative time in space. The Orbiter structural material, RCC, a reinforced carbon-carbon laminate with a diffused silicon carbide coating, is evaluated in terms of its resistance to hypervelocity impact. It was found that the specimens (disks with a mass of 34 g and a thickness of 5.0 mm) were cratered only on the front surface when the impact energy was 3 J or less. At 3 J, a trace of the black carbon interior was exposed. The specimens were completely penetrated when the energy was 34 J or greater.

The concept of generalized enzyme reactions suggests that a wide variety of substrates can undergo enzymatic transformations, including those whose biotransformation has not yet been realized. The use of quantum chemistry to evaluate kinetic feasibility is an attractive approach to identify enzymes for the proposed transformation. However, the sheer number of novel transformations that can be generated makes this impractical as a screening approach. Therefore, it is essential to develop structure/activity relationships based on quantities that are more efficient to calculate. In this work, we propose a structure/activity relationship based on the free energy of binding or reaction of non-native substrates to evaluate the catalysis relative to that of native substrates. While Broensted-Evans-Polanyi (BEP) relationships such as that proposed here have found broad application in heterogeneous catalysis, their extension to enzymatic catalysis is limited. We report here on density functional theory (DFT) studies for C-C bond formation and C-C bond cleavage associated with the decarboxylation of six 2-keto acids by a thiamine-containing enzyme (EC 1.2.7.1) and demonstrate a linear relationship between the free energy of reaction and the activation barrier. We then applied this relationship to predict the activation barriers of 17 chemically similar novel reactions. These calculations reveal that there is a clear correlation between the free energy of formation of the transition state and the free energy of the reaction, suggesting that this method can be further extended to predict the kinetics of novel reactions through our computational framework for discovery of novel biochemical transformations.

The concept of generalized enzyme reactions suggests that a wide variety of substrates can undergo enzymatic transformations, including those whose biotransformation has not yet been realized. The use of quantum chemistry to evaluate kinetic feasibility is an attractive approach to identify enzymes for the proposed transformation. However, the sheer number of novel transformations that can be generated makes this impractical as a screening approach. Therefore, it is essential to develop structure/activity relationships based on quantities that are more efficient to calculate. In this work, we propose a structure/activity relationship based on the free energy of binding or reaction of non-native substrates to evaluate the catalysis relative to that of native substrates. While Brønsted-Evans-Polanyi (BEP) relationships such as that proposed here have found broad application in heterogeneous catalysis, their extension to enzymatic catalysis is limited. We report here on density functional theory (DFT) studies for C–C bond formation and C–C bond cleavage associated with the decarboxylation of six 2-keto acids by a thiamine-containing enzyme (EC 1.2.7.1) and demonstrate a linear relationship between the free energy of reaction and the activation barrier. We then applied this relationship to predict the activation barriers of 17 chemically similar novel reactions. These calculations reveal that there is a clear correlation between the free energy of formation of the transition state and the free energy of the reaction, suggesting that this method can be further extended to predict the kinetics of novel reactions through our computational framework for discovery of novel biochemical transformations.

The mechanism of formation of [FeIV(O)(N4Py)]2+ (2, N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) from the reaction of [FeII(N4Py)(CH3CN)]2+ (1) with m-chloroperbenzoic acid (mCPBA) in CH2Cl2 at −30 °C has been studied on the basis of the visible spectral changes observed and the reaction stoichiometry. It is shown that the conversion of 1 to 2 in 90% yield requires 1.5 equiv peracid and takes place in two successive one-electron steps via an [FeIII(N4Py)OH]2+(3) intermediate. The first oxidation step uses 0.5 equiv peracid and produces 0.5 equiv 3-chlorobenzoic acid, while the second step uses 1 equiv peracid and affords byproducts derived from chlorophenyl radical. We conclude that the FeII(N4Py) center promotes O-O bond heterolysis, while the FeIII(N4Py) center favors O-O bond homolysis, so the nature of O-O bond cleavage is dependent on the iron oxidation state. PMID:18443654

The molecular structure of 3-(ortho-methoxyphenylthio) pentane-2,4-dione (o-MPTPD) and 3-(para-methoxyphenylthio) pentane-2,4-dione (p-MPTPD) has been investigated by means of Density Functional Theory (DFT) calculations. The results were compared with 3-(phenylthio) pentane-2,4-dione (PTPD), 3-(methylthio) pentane-2,4-dione (MTPD), and their parent, pentane-2,4-dione (known as acetylacetone, AA). The full optimized geometry, the IR and Raman frequencies and their intensities has been calculated at the B3LYP/6-311++G∗∗ level of theory. The calculated frequencies were compared with the experimental results. The IR and Raman spectra of o-MPTPD and p-MPTPD and their deuterated analogs are recorded in the 3200-200 cm-1 range. The quantum theory of atoms in molecules (QTAIM) was applied to calculate the topological parameters of electron density distributions and charge transfer energy associated with the intramolecular hydrogen bond (IHB). Natural bond orbital analysis (NBO) was performed for investigation of electron delocalization in these compounds. According to the theoretical and experimental data, the hydrogen bond strength in the 3-thio-pentane-2,4-dione derivatives is much stronger than that in AA. The results of theoretical calculations are in excellent agreement with the vibrational and NMR spectroscopy data.

In a Stirling radioisotope system, heat must continually be removed from the General Purpose Heat Source (GPHS) modules to maintain the modules and surrounding insulation at acceptable temperatures. The Stirling converter normally provides this cooling. If the Stirling convertor stops in the current system the insulation is designed to spoil, preventing damage to the GPHS at the cost of an earlier termination of the mission. An alkali-metal Variable Conductance Heat Pipe (VCHP) can be used to allow multiple stops and restarts of the Stirling convertor. A sodium VCHP with a Haynes 230 envelope was designed and fabricated for the Advanced Stirling Radioisotope Generator (ASRG), with a baseline 850° C heater head temperature. When the Stirling convertor is stopped, the heat from the GPHS is rejected to the Cold Side Adapter Flange using a low-mass, carbon-carbon radiator. The VCHP is designed to activate with a AT of 30° C. The 880° C temperature when the Stirling convertor is stopped is high enough to avoid risking standard ASRG operation, but low enough to save most of the heater head life. The VCHP has low mass and low thermal losses for normal operation. The design has been modified from an earlier, stainless steel prototype with a nickel radiator. In addition to replacing the nickel radiator with a low mass carbon-carbon radiator, the radiator location has been moved from the ASRG case to the cold side adapter flange. This flange already removes two-thirds of the heat during normal operation, so it is optimized to transfer heat to the case. The VCHP was successfully tested with a turn-on ΔT of 30° C in three orientations: horizontal, gravity-aided, and against gravity.

In crystalline state 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (chloranilic acid, CLA) forms with 4,4'-di-t-butyl-2,2'-bipyridyl (dtBBP) the hydrogen bonded chains along the b-axis. From one side of the CLA molecule the proton transfer takes place and the hydrogen bond length is very short (2.615 Å). A continuous infrared absorption is observed for dtBBP·CLA in the wavenumber range between 3100 and 800 cm -1 also indicating the strong hydrogen bonds. The DSC measurements show a weak, close to continuous, phase transition at 414 K. The complex dielectric permittivity for a single crystal sample was measured in the temperature range 100-440 K and at frequencies between 200 Hz and 2 MHz. The dielectric response is a combination of semiconducting properties and a relaxation process most probably connected with the proton dynamics in the hydrogen bonds. The mechanism of the structural phase transition is discussed.

Research on three classes of materials that show potential for allowing significant increases in operating temperatures in gas turbine engines is discussed. Monolithic ceramics, ceramic matrix composites, and carbon-carbon composites are discussed. Sintering, hot pressing, and densification are discussed.

Sputter yields have been measured for polycrystalline diamond, single crystal diamond, a carbon-carbon composite, and molybdenum subject to bombardment with xenon. The tests were performed using a 3 cm Kaufman ion source to produce incident ions with energy in the range of 150 - 750 eV and profilometry based technique to measure the amount of sputtered material.

Although many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. However, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree-Fock method have been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive

A systematic, ab initio electronic structure analysis of the strong, positive-ion hydrogen bond is reported. Energies and wave functions have been obtained at the 4-31G level for the twenty-one complexes, (BṡṡṡH-A)+, where A,B=NH3, OH2, FH, PH3, SH2, ClH. The A-H bond length (r1), the BṡṡṡA separation (R(, and the angle (ϑ) measured relative to the symmetry axis of B have been optimized. Calculated dimerization energies ED are found to be in reasonable agreement with experiment. Charge density difference plots of these complexes exhibit a remarkable similarity to the pattern of alternating charge gain and loss known for the neutral H-bonded dimers. The proton donor is characterized by a charge gain region between A and the proton and charge loss on the proton; the electron donor by a charge loss between B and the proton. Four of the complexes (HFṡṡṡHṡṡṡFH)+, (H2OṡṡṡHṡṡṡOH2)+, (HClṡṡṡHṡṡṡClH)+, (HClṡṡṡHṡṡṡFH)+, have unusually short internuclear separations and show large charge gain around the protons. This is the first theoretical evidence of a transition from predominantly electrostatic to predominantly covalent binding in hydrogen bonding and it corroborates a recent experimental X-N study. An estimate of the amount of charge lost from the proton, ΔqH, has been obtained from the difference plots and is found to bear a linear relation with the dimerization energy ED for a series of complexes with a single proton donor. The inverse relation between ED and the difference in monomer proton affinities, ΔPA, reported in the literature for substituted pyridinium ions, is shown to hold as well for all A and B. Our calculated results also give a quantitative demonstration of the recently proposed inverse relationship between proton position and ΔPA. Several useful new organizing principles have been found: (a) R varies linearly with r2, the BṡṡṡH distance. Covalent bonding in the four complexes noted

Institutional bonding was examined at a public, urban commuter college with exceptionally high attrition and visibly low morale. Changes in bonding and attrition were measured 6 years after a 2-year effort to develop school identity and student feelings of membership. It was found that a simple index of campus morale is provided by level of…

In this paper, we deal with suitable generalizations of the notion of bond between contexts, as part of the research area of Formal Concept Analysis. We study different generalizations of the notion of bond within the ? -fuzzy setting. Specifically, given a formal context, there are three prototypical pairs of concept-forming operators, and this immediately leads to three possible versions of the notion of bond (so-called homogeneous bond wrt certain pair of concept-forming operators). The first results show a close correspondence between a homogeneous bond between two contexts and certain special types of mappings between the sets of extents (or intents) of the corresponding concept lattices. Later, we introduce the so-called heterogeneous bonds (considering simultaneously two types of concept-forming operators) and generalize the previous relationship to mappings between the sets of extents (or intents) of the corresponding concept lattices.

We study the stability of various kinds of graphene samples under soft x-ray irradiation. Our results show that in single-layer exfoliated graphene (a closer analog to two-dimensional material), the in-plane carbon-carbonbonds are unstable under x-ray irradiation, resulting in nanocrystalline structures. As the interaction along the third dimension increases by increasing the number of graphene layers or through the interaction with the substrate (epitaxial graphene), the effect of x-ray irradiation decreases and eventually becomes negligible for graphite and epitaxial graphene. Our results demonstrate the importance of the interaction along the third dimension in stabilizing the long range in-plane carbon-carbonbonding, and suggest the possibility of using x-ray to pattern graphene nanostructures in exfoliated graphene.

A method of improving the bonding characteristics of a previously bonded silicon on insulator (SOI) structure is provided. The improvement in the bonding characteristics is achieved in the present invention by, optionally, forming an oxide cap layer on the silicon surface of the bonded SOI structure and then annealing either the uncapped or oxide capped structure in a slightly oxidizing ambient at temperatures greater than 1200.degree. C. Also provided herein is a method for detecting the bonding characteristics of previously bonded SOI structures. According to this aspect of the present invention, a pico-second laser pulse technique is employed to determine the bonding imperfections of previously bonded SOI structures.

Recently, it was shown that μ-oxo-μ-peroxodiiron(III) is converted to high-spin μ-oxodioxodiiron(IV) through O-O bond scission. Herein, the formation and high reactivity of the anti-dioxo form of high-spin μ-oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic-absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ-oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is tolueneformed by syn-to-anti transformation of the syn-dioxo form and reacts with substrates as the oxidant. The anti-dioxo form is 620 times more reactive in the C-H bond cleavage of ethylbenzene than the most reactive diiron system reported so far. The KIE for the reaction with toluene/[D8 ]toluene is 95 at -30 °C, which the largest in diiron systems reported so far. The present diiron complex efficiently catalyzes the oxidation of various alkanes with H2 O2 . PMID:26970337

Solubility of Ethyne in Liquids was published in 2001 as Vol. 76 of the IUPAC-NIST Solubility Data Series. The current work extends the coverage to the solubility in liquids of higher gaseous and liquid acetylenes and to derivatives that contain a triple carbon-carbonbond. Predictive methods for estimating solubilities in water are summarised and usually give values to within an order of magnitude. The literature has been surveyed to the end of 2010.

Many carbon-carbon composite aircraft brakes encounter high wear rates during low energy braking operations. The work presented in this thesis addresses this issue, but it also elucidates the microstructural changes and wear mechanisms that take place in these materials during all braking conditions encountered by aircraft brakes. A variety of investigations were conducted using friction and wear testing, as well as examination of wear surfaces and wear debris using OM, SEM, X-RD, TGA and Density Gradient Separation (DOS). Friction and wear tests were conducted on a PAN fibre/CVI matrix carbon-carbon composite (Dunlop) and a pitch fibre/Resin-CVI matrix carbon-carbon composite (Bendix). Extensive testing was undertaken on the Dunlop composites to asses the effects of composite architecture, fibre orientation and heat treatment temperatures on friction and wear. Other friction and wear tests, conducted on the base Dunlop composite, were used to investigate the relative influences of temperature and sliding speed. It was found that the effect of temperature was dominant over composite architecture, fibre orientation and sliding speed in governing the friction and wear performance of the Dunlop composites. The development of bulk temperatures in excess of 110 C by frictional heating resulted in smooth friction and a low wear rate. Reducing heat treatment temperature also reduced the thermal conductivity producing high interface temperatures, low smooth friction coefficients and low wear rates under low energy braking conditions. However, this was at the expense of high oxidative wear rates under higher energy braking conditions. The Bendix composites had lower thermal conductivities than the fully heat treated Dunlop composite and exhibited similar friction and wear behaviour to Dunlop composites heat treated to lower temperatures. Examination of the wear surfaces using OM and SEM revealed particulate or Type I surface debris on wear surfaces tested under low energy

Summary A series of novel benzimidazolium salts (1–4) and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI) themed palladium N-heterocyclic carbene complexes [PdCl2(NHC)(Py)] (5–8), where NHC = 1-(N-methylphthalimide)-3-alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of 1H and 13C{1H} NMR, UV–vis (for 5–8), ESI-FTICR-MS (for 2, 4, 6–8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki–Miyaura cross-coupling (for 1–8) and arylation (for 5–8) reactions. As catalysts, they demonstrated a highly efficient route for the formation of asymmetric biaryl compounds even though they were used in very low loading. For example, all compounds displayed good catalytic activity for the C–C bond formation of 4-tert-butylphenylboronic acid with 4-chlorotoluene. PMID:26877810

The use of selective metal chelating agents with preference for binding of a specific metal ion to investigate its biological role is becoming increasingly common. We found recently that a well-known copper-specific chelator 2,9-dimethyl-1,10-phenanthroline (2,9-Me2OP) could completely inhibit the synergistic toxicity induced by tetrachlorocatechol (TCC) and sodium azide (NaN3). However, its underlying molecular mechanism is still not clear. Here, we show that the protection by 2,9-Me2OP is not due to its classic copper-chelating property, but rather due to formation of a multiple hydrogen-bonded complex between 2,9-Me2OP and TCC, featuring an unusual perpendicular arrangement of the two binding partners. The two methyl groups at the 2,9 positions in 2,9-Me2OP were found to be critical to stabilize the 2,9-Me2OP/TCC complex due to steric hindrance, and therefore completely prevents the generation of the reactive and toxic semiquinone radicals by TCC/NaN3. This represents the first report showing that an unexpected new protective mode of action for the copper "specific" chelating agent 2,9-Me2OP by using its steric hindrance effect of the two CH3 groups not only to chelate copper, but also to "chelate" a catechol through multiple H-bonding. These findings may have broad biological implications for future research of this widely used copper-chelating agent and the ubiquitous catecholic compounds. PMID:25125348

Lignin is an abundant natural resource that is a potential source of valuable chemicals. Improved understanding of the pyrolysis of lignin occurs through the study of model compounds for which phenethyl phenyl ether (PhCH2CH2OPh, PPE) is the simplest example representing the dominant -O-4 ether linkage. The initial step in the thermal decomposition of PPE is the homolytic cleavage of the oxygen-carbon bond. The rate of this key step will depend on the bond dissociation enthalpy, which in turn will depend on the nature and location of relevant substituents. We used modern density functional methods to calculate the oxygen-carbon bond dissociation enthalpies for PPE and several oxygen substituted derivatives. Since carbon-carbonbond cleavage in PPE could be a competitive initial reaction under high temperature pyrolysis conditions, we also calculated substituent effects on these bond dissociation enthalpies. We found that the oxygen-carbon bond dissociation enthalpy is substantially lowered by oxygen substituents situated at the phenyl ring adjacent to the ether oxygen. On the other hand, the carbon-carbonbond dissociation enthalpy shows little variation with different substitution patterns on either phenyl ring.

Lignin is an abundant natural resource that is a potential source of valuable chemicals. Improved understanding of the pyrolysis of lignin occurs through the study of model compounds for which phenethyl phenyl ether (PhCH(2)CH(2)OPh, PPE) is the simplest example representing the dominant beta-O-4 ether linkage. The initial step in the thermal decomposition of PPE is the homolytic cleavage of the oxygen-carbon bond. The rate of this key step will depend on the bond dissociation enthalpy, which in turn will depend on the nature and location of relevant substituents. We used modern density functional methods to calculate the oxygen-carbon bond dissociation enthalpies for PPE and several oxygen-substituted derivatives. Since carbon-carbonbond cleavage in PPE could be a competitive initial reaction under high-temperature pyrolysis conditions, we also calculated substituent effects on these bond dissociation enthalpies. We found that the oxygen-carbon bond dissociation enthalpy is substantially lowered by oxygen substituents situated at the phenyl ring adjacent to the ether oxygen. On the other hand, the carbon-carbonbond dissociation enthalpy shows little variation with different substitution patterns on either phenyl ring. PMID:19260664

Nanostructured carbon, in the form of tubes or sheets, exhibits exceptional thermal and electrical properties. Graphene, a single atomic sheet of hexagonal sp2 bonded carbon, posesses a thermal conductivity higher than diamond, with an extremely high electron mobility. Carbon nanotubes (CNT), which are tubes composed of one or more graphene sheets, also posess high thermal conductivity and electron mobility. One of the major problems facing the application of nanomaterials is integration into already existing material systems. A second challenge is controlled synthesis of nanomaterials. In this dissertation research novel methods were investigated for coupling carbon nanotubes to polymer matrices, as well as new approaches for controlling the synthesis of graphene and reduced graphene oxide like carbon (R-GOC) on copper (Cu) foils via chemical vapor deposition. It was determined that carboxylic functionalization of carbon nanotubes was effective in improving the coupling of CNTs to polymer matrices, affecting the thermal transport of the resulting CNT-polymer nanocomposites. From the CVD studies it was established that the cooling phase gases flowed after deposition influence the growth mechanics of graphene on Cu foil. Further CVD studies showed that methane may be decomposed directly onto quartz to form reduced graphene oxide like carbon thin films. The obtained thermal characterization results are important for development of CNTs as fillers for composite pastes with high thermal conductivity, and the results of the CVD studies are important for developing further understanding of growth mechanics of bilayer graphene and other nanostructured carbon. In addition to the fundamental study of CVD synthesis of graphene and R-GOC, this dissertation work includes engineering of graphene and R-GOC to various applications, including the development of the thinnest flexible transistor with active materials made from all-2D materials, as well as large-scale electron

The goal was to manufacture carbon/carbon (C/C) composites through a unique procedure with improved biocompatibility and reduced debris release. C/C composites were prepared by chemical vapor deposition, and their biological properties were analyzed. With regard to mechanical properties, compressive strength/modulus was 219.1 MPa/9.72 GPa, flexural strength/modulus was 121.63 MPa/21.9 GPa, and interlaminar sheer was 15.13 GPa. Biocompatibility testing revealed: (1) the extract liquid from the C/C composites had no effect on cell proliferation; (2) the extract had no impact on micronucleus frequency as compared with the control groups (P > 0.05); (3) in vivo, there was mild tissue inflammation after implantation within the first 2 weeks, but there was no significant difference compared with the control group (P > 0.05); (4) the implants were well integrated into the host tissue, and debris was limited. The tested samples have excellent biocompatibilities and reduced release of debris. The demonstrated changes in manufacturing procedures are promising. PMID:19593650

This document consists of the entire test database generated to support the Reinforced Carbon-Carbon Transatlantic Abort Landing Study. RCC components used for orbiter nose cap and wing leading edge thermal protection were originally designed to have a multi-mission entry capability of 2800 F. Increased orbiter range capability required a predicted increase in excess of 3300 F. Three test series were conducted. Test series #1 used ENKA-based RCC specimens coated with silicon carbide, treated with tetraethyl orthosilicate, sealed with Type A surface enhancement, and tested at 3000-3400 F with surface pressure of 60-101 psf. Series #2 used ENKA- or AVTEX-based RCC, with and without silicon carbide, Type A or double Type AA surface enhancement, all impregnated with TEOS, and at temperatures from 1440-3350 F with pressures from 100-350 psf. Series #3 tested ENKA-based RCC, with and without silicon carbide coating. No specimens were treated with TEOS or sealed with Type A. Surface temperatures ranged from 2690-3440 F and pressures ranged from 313-400 psf. These combined test results provided the database for establishing RCC material single-mission-limit temperature and developing surface recession correlations used to predict mass loss for abort conditions.

In this research, it is demonstrated that the integration of nondestructive evaluation with the finite element method (a quantitative NDE/FEM approach) can be used for analysis and behavior prediction of advanced materials, such as fiber composites, after processing and during in-service testing. First, stress, strain, and energy data were calculated by the finite element method for square plates with a 10 percent difference in the material properties between specified segments, i.e., between the center and the outside section or between two halves of the plate. This demonstrated the efficiency of the method in predicting variations in the structural behavior based on small material property differences. Then, finite element analyses and actual axial compression tests were performed on a Space Shuttle brake stator made from woven carbon-carbon composites. The material properties used in the numerical modeling of the stator were previously characterized at a large number of points on the component by quantitative NDE-procedures, i.e., ultrasonics and radiography. The results from the experimental compressive loading tests were used to verify the NDE/FEM results. Good agreement was found for most parameters.

Thermographic nondestructive inspection techniques have been shown to provide quantitative, large area damage detection capabilities for the ground inspection of the reinforced carbon-carbon (RCC) used for the wing leading edge of the Shuttle orbiter. The method is non-contacting and able to inspect large areas in a relatively short inspection time. Thermal nondestructive evaluation (NDE) inspections have been shown to be applicable for several applications to the Shuttle in preparation for return to flight, including for inspection of RCC panels during impact testing, and for between-flight orbiter inspections. The focus of this work is to expand the capabilities of the thermal NDE methodology to enable inspection by an astronaut during orbital conditions. The significant limitations of available resources, such as weight and power, and the impact of these limitations on the inspection technique are discussed, as well as the resultant impact on data analysis and processing algorithms. Of particular interest is the impact to the inspection technique resulting from the use of solar energy as a heat source, the effect on the measurements due to working in the vacuum of space, and the effect of changes in boundary conditions, such as radiation losses seen by the material, on the response of the RCC. The resultant effects on detectability limits are discussed. Keywords: Nondestructive Evaluation, Shuttle, on-orbit inspection, thermography, infrared

The potential of carbon-carbon (CC) composites as materials for high temperature applications was recognized at a very early stage, leading to their development in the 1960`s as materials for thermal protection during space vehicle re-entry. By the early 1970`s, two basic approaches to the formation of the carbon matrix were established, namely through chemical vapor deposition from a hydrocarbon gas (CVD) and through carbonization of a carbon-bearing resin or pitch. Fundamentally, little has changed since those early years with respect to these basic methods of CC composite fabrication. Further developments have, however, involved the introduction of multidirectional fibre architectures in order to reduce the mechanical anisotropy present in unidirectionally and bidirectionally reinforced composites caused by poor mechanical properties in the unreinforced directions. The strategic importance of several aerospace applications of CC composites, including military rocket nozzles and nose cones, the NASA space shuttle nose cone and leading edge protection surfaces, aircraft brake discs and gas diverter fins, ensured their continued development during the 1970`s and 1980`s.

Carbon-based ion optics have the potential to significantly increase the operable life and power ranges of ion thrusters because of reduced erosion rates compared to molybdenum optics. The development of 15-cm and larger diameter grids has encountered many problems, however, not the least of which is the ability to pass vibration testing. JPL has recently developed a new generation of 30-cm carbon-carbon ion optics in order to address these problems and demonstrate the viability of the technology. Perveance, electron backstreaming, and screen grid transparency data are presented for two sets of optics. Vibration testing was successfully performed on two different sets of ion optics with no damage and the results of those tests are compared to models of grid vibrational behavior. It will be shown that the vibration model is a conservative predictor of grid response and can accurately describe test results. There was no change in grid alignment as a result of vibration testing and a slight improvement, if any change at all, in optics performance.

Refractory-composite/heat-pipe-cooled wing an tail leading edges are being considered for use on hypersonic vehicles to limit maximum temperatures to values below material reuse limits and to eliminate the need to actively cool the leading edges. The development of a refractory-composite/heat-pipe-cooled leading edge has evolved from the design stage to the fabrication and testing of heat pipes embedded in carbon/carbon (C/C). A three-foot-long, molybdenum-rhenium heat pipe with a lithium working fluid was fabricated and tested at an operating temperature of 2460 F to verify the individual heat-pipe design. Following the fabrication of this heat pipe, three additional heat pipes were fabricated and embedded in C/C. The C/C heat-pipe test article was successfully tested using quartz lamps in a vacuum chamber in both a horizontal and vertical orientation. Start up and steady state data are presented for the C/C heat-pipe test article. Radiography and eddy current evaluations were performed on the test article.

Using 2.5-dimensional carbon fiber fabrics as the reinforcement, porous carbon/carbon(C/C) substrates were firstly fabricated by impregnation/carbonization (I/C) technique with furan resin and then treated at 2000, 2300 and 3000 °C, respectively. Finally, carbon fiber reinforced carbon and copper(C/C-Cu) composites were prepared by infiltrating melt copper alloy into C/C substrates under pressure. The effects of treating temperatures on microstructures and thermal conductivities of the composites were investigated. The results show that heat treatment plays an important role in the microstructure and thermal conductivity of C/C-Cu composites. It is conducive not only to rearrange the carbon crystallite of resin-based carbon in oriented layer structure, but also to improve the content and connectivity of copper alloy. The thermal conductivity increases with the increase in heat treatment temperature in both parallel and perpendicular direction; the thermal conductivity in parallel direction is evidently superior to that in perpendicular direction.

... drawback under the provisions of this subpart until a bond on TTB Form 5154.3 has been approved. ... United States from Puerto Rico and intending to file monthly claims for drawback under the provisions of this subpart shall obtain a bond on Form 5154.3. When the limit of liability under a bond given in...

... drawback under the provisions of this subpart until a bond on TTB Form 5154.3 has been approved. ... United States from Puerto Rico and intending to file monthly claims for drawback under the provisions of this subpart shall obtain a bond on Form 5154.3. When the limit of liability under a bond given in...

... drawback under the provisions of this subpart until a bond on TTB Form 5154.3 has been approved. ... United States from Puerto Rico and intending to file monthly claims for drawback under the provisions of this subpart shall obtain a bond on Form 5154.3. When the limit of liability under a bond given in...

... drawback under the provisions of this subpart until a bond on TTB Form 5154.3 has been approved. ... United States from Puerto Rico and intending to file monthly claims for drawback under the provisions of this subpart shall obtain a bond on Form 5154.3. When the limit of liability under a bond given in...

... drawback under the provisions of this subpart until a bond on TTB Form 5154.3 has been approved. ... United States from Puerto Rico and intending to file monthly claims for drawback under the provisions of this subpart shall obtain a bond on Form 5154.3. When the limit of liability under a bond given in...

We report here a comprehensive understanding of the first C-C coupling during the induction period of the methanol-to-olefin process using density functional theory with the HSE06 hybrid functional. We illustrate the possible routes of formation for the active carbenium ion (CH3OCH2(+)), which has been identified to play an important part in triggering the formation of the first C-C bond and the hydrocarbon pool species. CH3OCH2(+) can be generated not only from dimethyl ether and Z(O)-CH3, but also from the reaction of HCHO and Z(O)-CH3, which has a lower effective barrier. An understanding of the dominance of CH3OCH2(+) over other carbocations and direct C-C coupling pathways is presented and quantitatively analysed. The charge distribution in the formation of CH3OCH2(+) is revealed and it is confirmed that the carbenium ion is thermodynamically more favoured than the radical. The subsequent reaction after the first C-C coupling was investigated, which uncovered some important active C2 species that possibly led to the formation of the active hydrocarbon pool intermediates and may finally realize the catalytic cycle. PMID:27173579

Initial estimates on the temperature and conditions of the breach in the Space Shuttle Columbia's wing focused on analyses of the slag deposits. These deposits are complex mixtures of the reinforced carbon/carbon (RCC) constituents, insulation material, and wing structural materials. Identification of melted/solidified Cerachrome insulation (Thermal Ceramics, Inc., Augusta, GA) indicated that the temperatures at the breach had exceeded 1760 C.

The energy change per electron in a chemical or physical transformation, ΔE/n, may be expressed as Δχ̅ + Δ(VNN + ω)/n, where Δχ̅ is the average electron binding energy, a generalized electronegativity, ΔVNN is the change in nuclear repulsions, and Δω is the change in multielectron interactions in the process considered. The last term can be obtained by the difference from experimental or theoretical estimates of the first terms. Previously obtained consequences of this energy partitioning are extended here to a different analysis of bonding in a great variety of diatomics, including more or less polar ones. Arguments are presented for associating the average change in electron binding energy with covalence, and the change in multielectron interactions with electron transfer, either to, out, or within a molecule. A new descriptor Q, essentially the scaled difference between the Δχ̅ and Δ(VNN + ω)/n terms, when plotted versus the bond energy, separates nicely a wide variety of bonding types, covalent, covalent but more correlated, polar and increasingly ionic, metallogenic, electrostatic, charge-shift bonds, and dispersion interactions. Also, Q itself shows a set of interesting relations with the correlation energy of a bond. PMID:26910496

For the first time, the influence of ultrasonically absorptive carbon-carbon material on hypersonic laminar to turbulent boundary layer transition was investigated experimentally. A 7° half-angle blunted cone with a nose radius of 2.5 mm and a total length of 1,077 mm was tested at zero angle of attack in the High Enthalpy Shock Tunnel Göttingen of the German Aerospace Center (DLR) at Mach 7.5. One-third of the metallic model surface in circumferential direction was replaced by DLR in-house manufactured ultrasonically absorptive carbon-carbon material with random microstructure for passive transition control. The remaining model surface consisted of polished steel and served as reference surface. The model was equipped with coaxial thermocouples to determine the transition location by means of surface heat flux distribution. Flush-mounted piezoelectric fast-response pressure transducers were used to measure the pressure fluctuations in the boundary layer associated with second-mode instabilities. The free-stream unit Reynolds number was varied over a range of Re m = 1.5 × 106 m-1 to Re m = 6.4 × 106 m-1 at a stagnation enthalpy of h 0 ≈ 3.2 MJ/kg and a wall temperature ratio of T w/ T 0 ≈ 0.1. The present study revealed a clear damping of the second-mode instabilities and a delay of boundary layer transition along the ultrasonically absorptive carbon-carbon insert.

The field of inquiry into how atoms are bonded together to form molecules and solids crosses the borderlines between physics and chemistry encompassing methods characteristic of both sciences. At one extreme, the inquiry is pursued with care and rigor into the simplest cases; at the other extreme, suggestions derived from the more careful inquiry…

The seco-B-ring bryostatin analogue, macrodiolide WN-1, was prepared in 17 steps (longest linear sequence) and 30 total steps with three bondsformed via hydrogen-mediated C-C coupling. This synthetic route features a palladium-catalyzed alkoxycarbonylation of a C2-symmetric diol to form the C9-deoxygenated bryostatin A-ring. WN-1 binds to PKCα (Ki = 16.1 nM) and inhibits the growth of multiple leukemia cell lines. Although structural features of the WN-1 A-ring and C-ring are shared by analogues that display bryostatin-like behavior, WN-1 displays PMA-like behavior in U937 cell attachment and proliferation assays, as well as in K562 and MV-4-11 proliferation assays. Molecular modeling studies suggest the pattern of internal hydrogen bonds evident in bryostatin 1 is preserved in WN-1, and that upon docking WN-1 into the crystal structure of the C1b domain of PKCδ, the binding mode of bryostatin 1 is reproduced. The collective data emphasize the critical contribution of the B-ring to the function of the upper portion of the molecule in conferring a bryostatin-like pattern of biological activity. PMID:25207655

The seco-B-ring bryostatin analogue, macrodiolide WN-1, was prepared in 17 steps (longest linear sequence) and 30 total steps with three bondsformed via hydrogen-mediated C–C coupling. This synthetic route features a palladium-catalyzed alkoxycarbonylation of a C2-symmetric diol to form the C9-deoxygenated bryostatin A-ring. WN-1 binds to PKCα (Ki = 16.1 nM) and inhibits the growth of multiple leukemia cell lines. Although structural features of the WN-1 A-ring and C-ring are shared by analogues that display bryostatin-like behavior, WN-1 displays PMA-like behavior in U937 cell attachment and proliferation assays, as well as in K562 and MV-4-11 proliferation assays. Molecular modeling studies suggest the pattern of internal hydrogen bonds evident in bryostatin 1 is preserved in WN-1, and that upon docking WN-1 into the crystal structure of the C1b domain of PKCδ, the binding mode of bryostatin 1 is reproduced. The collective data emphasize the critical contribution of the B-ring to the function of the upper portion of the molecule in conferring a bryostatin-like pattern of biological activity. PMID:25207655

Chiral ruthenium(II) complexes modified by Josiphos ligands catalyze the reaction of alkynes with primary alcohols to form homoallylic alcohols with excellent control of regio-, diastereo- and enantioselectivity. These processes represent the first examples of enantioselective carbonyl allylation using alkynes as allylmetal equivalents. PMID:25734220

Disclosed is a process for production of soldered joints which are highly reliable and capable of surviving 10,000 thermal cycles between about [minus]40 C and 110 C. Process involves interposing a thin layer of a metal solder composition between the metal surfaces of members to be bonded and applying heat and up to about 1000 psi compression pressure to the superposed members, in the presence of a reducing atmosphere, to extrude the major amount of the solder composition, contaminants including fluxing gases and air, from between the members being bonded, to form a very thin, strong intermetallic bonding layer having a thermal expansion tolerant with that of the bonded members.

Production of soldiered joints which are highly reliable and capable of surviving 10,000 thermal cycles between about {minus}40{degrees}C and 110{degrees}C. Process involves interposing a thin layer of a metal solder composition between the metal surfaces of members to be bonded and applying heat and up to about 1000 psi compression pressure to the superposed members, in the presence of a reducing atmosphere, to extrude the major amount of the solder composition, contaminants including fluxing gases and air, from between the members being bonded, to form a very thin, strong intermetallic bonding layer having a thermal expansion tolerant with that of the bonded members.

Production of soldered joints which are highly reliable and capable of surviving 10,000 thermal cycles between about -40.degree. C. and 110.degree. C. Process involves interposing a thin layer of a metal solder composition between the metal surfaces of members to be bonded and applying heat and up to about 1000 psi compression pressure to the superposed members, in the presence of a reducing atmosphere, to extrude the major amount of the solder composition, contaminants including fluxing gases and air, from between the members being bonded, to form a very thin, strong intermetallic bonding layer having a thermal expansion tolerant with that of the bonded members.

Structurally stronger titanium articles are produced by a weld-bonding technique comprising fastening at least two plates of titanium together using spotwelding and curing an adhesive interspersed between the spot-weld nuggets. This weld-bonding may be employed to form lap joints or to stiffen titanium metal plates.

Silver triflate and copper(I) iodide cocatalyzed direct alkynylation and cyclization reaction of in situ formed N-iminoisoquinolinium ylides with bromoalkynes is described. The reaction proceeds efficiently through a combination of C-H activation and subsequent tandem reaction in one pot, leading to diverse H-pyrazolo[5,1-a]isoquinolines in good yields under mild reaction conditions. PMID:22946742

Highlights: {yields} The CNFs improve the infiltration rate and thermal properties of carbon/carbon composites. {yields} The densification rate increases with the CNF content increasing at the beginning of infiltration. {yields} The values of the thermal conductivity of the composite obtain their maximum values at 5 wt.%. -- Abstract: Preforms containing 0, 5, 10, 15 and 20 wt.% carbon nanofibers (CNFs) were fabricated by spreading layers of carbon cloth, and infiltrated using the electrified preform heating chemical vapor infiltration method (ECVI) under atmospheric pressure. Initial thermal gradients were determined. Resistivity and density evolutions with infiltration time have been recorded. Scanning electron microscopy, polarized light micrograph and X-ray diffraction technique were used to analyze the experiment results. The results showed that the infiltration rate increased with the rising of CNF content, and after 120 h of infiltration, the density was the highest when the CNF content was 5 wt.%, but the composite could not be densified efficiently as the CNF content ranged from 10 wt.% to 20 wt.%. CNF-reinforced C/C composites have enhanced thermal conductivity, the values at 5 wt.% were increased by nearly 5.5-24.1% in the X-Y direction and 153.8-251.3% in the Z direction compared to those with no CNFs. When the additive content was increased to 20 wt.%, due to the holes and cavities in the CNF web and between carbon cloth and matrix, the thermal conductivities in the X-Y and Z directions decreased from their maximum values at 5 wt.%.

Following the tragedy of the Space Shuttle Columbia on February 1, 2003, a major effort commenced to develop a better understanding of debris impacts and their effect on the Space Shuttle subsystems. An initiative to develop and validate physics-based computer models to predict damage from such impacts was a fundamental component of this effort. To develop the models it was necessary to physically characterize Reinforced Carbon-Carbon (RCC) and various debris materials which could potentially shed on ascent and impact the Orbiter RCC leading edges. The validated models enabled the launch system community to use the impact analysis software LS DYNA to predict damage by potential and actual impact events on the Orbiter leading edge and nose cap thermal protection systems. Validation of the material models was done through a three-level approach: fundamental tests to obtain independent static and dynamic material model properties of materials of interest, sub-component impact tests to provide highly controlled impact test data for the correlation and validation of the models, and full-scale impact tests to establish the final level of confidence for the analysis methodology. This paper discusses the second level subcomponent test program in detail and its application to the LS DYNA model validation process. The level two testing consisted of over one hundred impact tests in the NASA Glenn Research Center Ballistic Impact Lab on 6 by 6 in. and 6 by 12 in. flat plates of RCC and evaluated three types of debris projectiles: BX 265 External Tank foam, ice, and PDL 1034 External Tank foam. These impact tests helped determine the level of damage generated in the RCC flat plates by each projectile. The information obtained from this testing validated the LS DYNA damage prediction models and provided a certain level of confidence to begin performing analysis for full-size RCC test articles for returning NASA to flight with STS 114 and beyond.

Carbon/Carbon (C/C) composites are used in high temperature applications because they exhibit excellent thermomechanical properties. There are several challenges associated with the processing of C/C composites that include long cycle times, formation of closed porosity within fabric woven architecture and carbonization induced cracks that can lead to reduction of mechanical properties. This work addresses various innovative approaches to reduce processing uncertainties and thereby improve thermomechanical properties of C/C by using vapor grown carbon nanofibers (VGCNFs) in conjunction with carbon fabric and precursor phenolic matrix. The different aspects of the proposed research contribute to understanding of the translation of VGCNFs properties in a C/C composite. The specific objectives of the research are; (a) To understand the mechanical properties and microstructural features of phenolic resin precursor with and without modification with VGCNFs; (b) To develop innovative processing concepts that incorporate VGCNFs by spraying them on carbon fabric and/or adding VGCNFs to the phenolic resin precursor; and characterizing the process induced thermal and mechanical properties; and (c) To develop a finite element model to evaluate the thermal stresses developed in the carbonization of carbon/phenolic with and without VGCNFs. Addition of VGCNFs to phenolic resin enhanced the thermal and physical properties in terms of flexure and interlaminar properties, storage modulus and glass transition temperature and lowered the coefficient of thermal expansion. The approaches of spraying VGCNFs on the fabric surface and mixing VGCNFs with the phenolic resin was found to be effective in enhancing mechanical and thermal properties of the resulting C/C composites. Fiber bridging, improved carbon yield and minimization of carbonization-induced damage were the benefits of incorporating VGCNFs in C/C composites. Carbonization induced matrix cracking predicted by the finite

Functional near-infrared (NIR) fluorophores have played a major role in the recent advances in bioimaging. However, the optical and physicochemical stabilities of NIR fluorophores in the biological and physiological environment are still a challenge. Especially, the ether linkage on the meso carbon of heptamethine core is fragile when exposed to serum proteins or other amine-rich biomolecules. To solve such a structural limitation, a rigid carbon-carbonbond was installed onto the framework of ether-linked NIR fluorophores through the Suzuki coupling. The robust fluorophores replaced as ZW800-1C and ZW800-3C displayed enhanced optical and chemical stability in various solvents and a 100% warm serum environment (> 99%, 24 h). The biodistribution and clearance of C-C coupled ZW800 compounds were almost identical to the previously developed oxygen-substituted ZW800 compounds. When conjugated with a small molecule ligand, ZW800-1C maintained the identical stable form in warm serum (>98%, 24 h), while ZW800-1A hydrolyzed quickly after 4 h incubation (34%, 24 h). PMID:25530846

Yankee and Euromarket bonds may soon find their way into the financing of power projects in Latin America. For developers seeking long-term commitments under build, own, operate, and transfer (BOOT) power projects in Latin America, the benefits are substantial.

Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bondingformed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water. PMID:27491849

We have carried out a periodic Kohn-Sham density functional theory investigation of the pathways by which carbon-carbonbonds could be formed during the electrochemical reduction of CO2 on Cu(100) using a model that includes the effects of the electrochemical potential, solvent, and electrolyte. The electrochemical potential was set by relating the applied potential to the Fermi energy and then calculating the number of electrons required by the simulation cell for that specific Fermi energy. The solvent was included as a continuum dielectric, and the electrolyte was described using a linearized Poisson-Boltzmann model. The calculated potential of zero charge for a variety of surfaces agrees with experiment to within a mean average error of 0.09 V, thereby validating the assumptions of the model. Analysis of the mechanism for C-C bond formation revealed that at low-applied potential, C-C bond formation occurs through a CO dimer. However, at high applied potentials, a large activation barrier blocks this pathway; therefore, C-C bond formation occurs through reaction of adsorbed CHO and CO. Rate parameters determined from our calculations were used to simulate the kinetics of ethene formation during the electrochemical reduction of CO over a Cu(100) surface. An excellent match was observed between previously reported measurements of the partial current for ethene formation as a function of applied voltage and the variation in the partial current for C-C bond formation predicted by our microkinetic model. The electrochemical model reported here is simple, fairly easy to implement, and involves only a small increase in computational cost over calculations neglecting the effects of the electrolyte and the applied field. Therefore, it can be used to study the effects of applied potential and electrolyte composition on the energetics of surface reactions for a wide variety of electrochemical reactions. PMID:27045040

Halogen bonding (XB) is being extensively explored for its potential use in advanced materials and drug design. Despite significant progress in describing this interaction by theoretical and experimental methods, the chemical nature remains somewhat elusive, and it seems to vary with the selected system. In this work we present a detailed DFT analysis of three-center asymmetric halogen bond (XB) formed between dihalogen molecules and variously 4-substituted 1,2-dimethoxybenzene. The energy decomposition, orbital, and electron density analyses suggest that the contribution of electrostatic stabilization is comparable with that of non-electrostatic factors. Both terms increase parallel with increasing negative charge of the electron donor molecule in our model systems. Depending on the orientation of the dihalogen molecules, this bifurcated interaction may be classified as 'σ-hole - lone pair' or 'σ-hole - π' halogen bonds. Arrangement of the XB investigated here deviates significantly from a recent IUPAC definition of XB and, in analogy to the hydrogen bonding, the term bifurcated halogen bond (BXB) seems to be appropriate for this type of interaction. PMID:25656525

1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphous carbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT

The solvent influence on the excited states, emission and absorption energies of the oxo for of barbituric acid was studied with experimental (UV and fluorescence spectra) and theoretical methods. The excited-state reaction paths of the out-pf-plane elongation of the Nsbnd H bond of the oxo form of barbituric acid were also investigated (TD DFT level) to the conical intersections mediating internal conversions to the ground state. The 1nσ* excited state was found to be the driven electronic state. We found that the increase of the polarity of the solvent reduces the 1nσ* excited state decay rate through a non-planar conical intersection and increases its energy. Thus, solvents with higher polarity disfavor the non-radiative decay through conical intersections.

The Euphorbiaceae produce a wide variety of bioactive diterpenoids. These include the lathyranes, which have received much interest due to their ability to inhibit the ABC transporters responsible for the loss of efficacy of many chemotherapy drugs. The lathyranes are also intermediates in the biosynthesis of range of other bioactive diterpenoids with potential applications in the treatment of pain, HIV and cancer. We report here a gene cluster from Jatropha curcas that contains the genes required to convert geranylgeranyl pyrophosphate into a number of diterpenoids, including the lathyranes jolkinol C and epi-jolkinol C. The conversion of casbene to the lathyranes involves an intramolecular carbon-carbon ring closure. This requires the activity of two cytochrome P450s that we propose form a 6-hydroxy-5,9-diketocasbene intermediate, which then undergoes an aldol reaction. The discovery of the P450 genes required to convert casbene to lathyranes will allow the scalable heterologous production of these potential anticancer drugs, which can often only be sourced in limited quantities from their native plant. PMID:27272333

To improve the oxidation resistance of the SiC-MoSi2 coating prepared by two-step pack cementation, a liquid Si infiltrating method was adopted to modify it. The phase composition and microstructure of the coatings were analyzed by XRD and SEM. The results show that the size and number of the cracks in the modified coating decreased evidently after infiltrating Si. The oxidation test results in air at 1773 K show that the mass loss of the SiC-MoSi2 coating coated carbon/carbon (C/C) composites was up to 1.18% after oxidation for 206 h, while that of the modified coating coated C/C composites was only 0.77% after oxidation for 460 h. The reason is that the cracks formed in the pack cementation process were partly sealed and there were no penetrable cracks in the modified coating. Therefore, there were no direct channels for the oxygen to diffuse into the C/C substrate.

Ground-state stationary points on the potential energy surface of the reaction CF22++H2O→OCF++HF+H+ were calculated using the density-functional theory hybrid method B3LYP and the ab initio coupled cluster singles and doubles with perturbative triples [CCSD(T)] algorithm. The calculations reveal a reaction mechanism involving two transition states. The first transition state involves the migration of one hydrogen within the primary collision complex and the second corresponds to the loss of a proton. The neutral HF molecular product is formed in its stable ground 1Σ state. Comparison of activation energies for the reactions of CF22+ with H2O and with D2O, calculated from Becke three parameter Lee-Yang-Parr (B3LYP) zero-point energies, slightly favor the H2O pathway by 0.04 and 0.07 eV for the first and second activations, respectively. Rate constant calculations using Rice-Ramsperger-Kassel-Marcus/quasiequilibrium theory also kinetically favor the H2O pathway in comparison with the D2O pathway. However, the magnitudes of the calculated rate constants are so large (1012-1014 s-1) that the differences between the rates of reaction of CF22+ with H2O and with D2O should not be distinguished by a crossed-beam time-of-flight mass spectrometer experiment. Indeed, the ion yields reported in this paper from new collision experiments between CF22+ and D2O showed no isotope effect when compared with previous data from collisions of CF22+ with H2O.

A combination of gas-phase 3D quadrupole ion trap mass spectrometry experiments and density functional theory (DFT) calculations have been used to examine the mechanism of thermal decomposition of fluorinated coinage metal carboxylates. The precursor anions, [CF(3)CO(2)MO(2)CCF(3)](-) (M = Cu, Ag and Au), were introduced into the gas-phase via electrospray ionization. Multistage mass spectrometry (MS(n)) experiments were conducted utilizing collision-induced dissociation, yielding a series of trifluoromethylated organometallic species and fluorides via the loss of CO(2), CF(2) or "CF(2)CO(2)". Carboxylate ligand loss was insignificant or absent in all cases. DFT calculations were carried out on a range of potentially competing fragmentation pathways for [CF(3)CO(2)MO(2)CCF(3)](-), [CF(3)CO(2)MCF(3)](-) and [CF(3)CO(2)MF](-). These shed light on possible products and mechanisms for loss of "CF(2)CO(2)", namely, concerted or step-wise loss of CO(2) and CF(2) and a CF(2)CO(2) lactone pathway. The lactone pathway was found to be higher in energy in all cases. In addition, the possibility of forming [CF(3)MCF(3)](-) and [CF(3)MF](-), via decarboxylation is discussed. For the first time the novel fluoride complexes [FMF](-), M = Cu, Ag and Au have been experimentally observed. Finally, the decomposition reactions of [CF(3)CO(2)ML](-) (where L = CF(3) and CF(3)CO(2)) and [CH(3)CO(2)ML](-) (where L = CH(3) and CH(3)CO(2)) are compared. PMID:22310991

A technique for determining the radiocarbon age of both organic-carbon and carbonate-carbon in the eggshell of the large flightless birds Genyornis newtoni (now extinct) and Dromaius novaehollandiae (extant emu) is presented here. Stepped combustion (for organic-carbon) and stepped acidification (for carbonate-carbon) were used to obtain multiple age determinations for each sample, from which an assessment of the reliability of the ages is possible. Analysis of a Genyornis newtoni eggshell fragment known to have an age considerably beyond the limit of radiocarbon dating has indicated that the backgrounds obtainable using this approach are 0.122±0.033 pMC for the organic-carbon fraction and 0.070±0.025 pMC for the carbonate-carbon fraction. These backgrounds suggest that finite ages up to 50,000-55,000 BP are readily achievable on eggshell using stepped combustion/acidification. Analysis of a single fragment of Genyornis eggshell from Williams Point, central South Australia, suggests that significant contamination of the organic-carbon fraction of the eggshell is possible, while ages for the carbonate fraction appear more reliable and indicate that the eggshell has an age of at least 49,000±2000 BP. A total of six analyses of single Genyornis newtoni and Dromaius novaehollandiae eggshell fragments from the Wood Point deposit in southern South Australia suggest ages for the samples of 41,000±800 and 37,900±700 BP, respectively, while an optically stimulated luminescence (OSL) sample from a location very close to the Genyornis sample has an age of 55±5 ka (1 σ). The OSL and calibrated radiocarbon ages for the Genyornis sample and the sand matrix overlap at two standard deviations, suggesting the most likely age for the eggshell and the sand matrix is ˜45 cal ka BP or earlier.

Hexafluoroisopropanol phenyl group functionalized materials have great potential in the application of gas-sensitive materials for nerve agent detection, due to the formation of strong hydrogen-bonding interactions between the group and the analytes. In this paper, take full advantage of ultra-large specific surface area and plenty of carbon-carbon double bonds and hexafluoroisopropanol phenyl functionalized graphene was synthesized through in situ diazonium reaction between -C=C- and p-hexafluoroisopropanol aniline. The identity of the as-synthesis material was confirmed by transmission electron microscopy, Raman spectroscopy, ultraviolet visible spectroscopy, X-ray photoelectron spectroscopy and thermo gravimetric analysis. The synthesis method is simply which retained the excellent physical properties of original graphene. In addition, the novel material can be assigned as an potential candidate for gas sensitive materials towards organophosphorus nerve agent detection.

Coated, reinforced carbon-carbon (RCC) is used for the leading edges of the space shuttle. The mass loss characteristics of RCC specimens coated with tetraethyl orthosilicate (TEOS) were determine for conditions which simulated the environment expected at the lug attachment area of the leading edge. Mission simulation included simultaneous application of load, temperature, and oxygen partial pressure. Maximum specimen temperature was 900 K (1160 F). Specimens were exposed for up to 80 simulated missions. Stress levels up to 6.8 MPa (980 psi) did not significantly affect the mass loss characteristics of the TEOS-coated RCC material. Mass loss was correlated with the bulk density of the specimens.